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Process for preparing hydrogen from deoiled asphalt employing combustion gasification and CO2 in-situ adsorption-enhanced water-gas shift reaction in in-furnace calcium-spraying circulating fluidized bed

A circulating fluidized bed and water-vapor shift technology, applied in hydrogen, chemical recovery, inorganic chemistry, etc., can solve problems such as low conversion rate and inability to produce hydrogen from solid raw materials

Inactive Publication Date: 2015-09-02
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Our many years of research have shown that: due to the water vapor shift reaction of CO 2 Adsorption enhancement effect, CO disproportionation or further oxidation to CO 2 The conversion rate will be very low, CO 2 It can only be derived from hydrogen production products. We disclosed the hydrogen production process of glycerol adsorption enhanced reforming in patent ZL201010248222.7, but it is only applicable to gas-liquid raw materials, and the purpose of hydrogen production cannot be achieved for solid raw materials.

Method used

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  • Process for preparing hydrogen from deoiled asphalt employing combustion gasification and CO2 in-situ adsorption-enhanced water-gas shift reaction in in-furnace calcium-spraying circulating fluidized bed

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Experimental program
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Effect test

Embodiment 1

[0023] According to the mass ratio of heavy oil residue primary feed and secondary feed of 1:6, the air used in the circulating fluidized bed is 1:1.2 according to the ratio of the number of oxygen moles in the air to the carbon moles in the primary feed of heavy oil residue, and the water vapor used According to the ratio of the moles of water vapor to the carbon moles in the heavy oil residue secondary feed is 5:1, the amount of limestone desulfurizer is 6% according to the mass ratio of its Ca content to the heavy oil residue secondary feed, the gasification agent The water vapor enters the circulating fluidized bed furnace at an angle of 25 degrees downwards and injects it into the nozzle to burn and gasify the heavy oil residue in the circulating fluidized bed, and the generated synthesis gas enters the water vapor shift reactor. Carbon, water vapor and nitrogen in the molar ratio C / H 2 O / N 2 It is 1.78 / 5.35 / 20.8, sent into the water vapor shift reactor, wherein the flow...

Embodiment 2

[0025] According to the mass ratio of heavy oil residue primary feed and secondary feed of 1:8, the air used in the circulating fluidized bed is 1:1.1 according to the ratio of the number of oxygen moles in the air to the carbon moles in the primary feed of heavy oil residue, and the water vapor used According to the ratio of moles of water vapor to carbon moles in the secondary feed of heavy oil residue is 6:1, the amount of limestone desulfurizer is 10% according to the mass ratio of its Ca content to the secondary feed of heavy oil residue, gasification agent The water vapor enters the circulating fluidized bed furnace at an angle of 30 degrees downwards and injects the nozzle to carry out the circulating fluidized bed combustion and gasification of the heavy oil residue, and the generated synthesis gas enters the water vapor shift reactor. Carbon, water vapor and nitrogen in the molar ratio C / H 2 O / N 2 It is 1.78 / 5.35 / 20.8, sent into the water vapor shift reactor, wherein...

Embodiment 3

[0027]According to the mass ratio of heavy oil residue primary feed and secondary feed of 1:7, the air used in the circulating fluidized bed is 1:1.2 according to the ratio of the number of oxygen moles in the air to the carbon moles in the primary feed of heavy oil residue, and the water vapor used According to the ratio of moles of water vapor to carbon moles in the secondary feed of heavy oil residue is 5:1, the amount of limestone desulfurizer is 8% according to the mass ratio of its Ca content to the secondary feed of heavy oil residue, gasification agent The water vapor enters the circulating fluidized bed furnace at an angle of 28 degrees downward and injects into the nozzle to burn and gasify the heavy oil residue in the circulating fluidized bed, and the generated synthesis gas enters the water vapor shift reactor. Carbon, water vapor and nitrogen in the molar ratio C / H 2 O / N 2 It is 1.78 / 5.35 / 20.8, sent to the water vapor shift reactor, wherein the flow rate of nitr...

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Abstract

The invention discloses a process for preparing hydrogen from deoiled asphalt employing combustion gasification and CO2 in-situ adsorption-enhanced water-gas shift reaction in an in-furnace calcium-spraying circulating fluidized bed. The process comprises the following steps: gradually expanding a conical circulating fluidized bed of a hearth, carrying out partial air combustion on the deoiled asphalt on the lower part of the circulating fluidized bed, releasing heat for water vapor gasification on most of deoiled asphalt material; spraying a limestone desulfurization agent into a furnace, and carrying out desulfurization in a circulating fluidized bed furnace; feeding a synthesis gas generated by the circulating fluidized bed into a moving bed reactor; carrying out CO2 in-situ adsorption-enhanced water-gas shift reaction to prepare hydrogen; setting a water-gas shift moving bed reactor and a regenerator through the adsorption-enhanced water-gas shift reaction, so that successive and simultaneous movement, reaction and regeneration of an NiO / Al2O3 catalyst and an CaO adsorbent of adsorbing CO2 are carried out. By virtue of coupling of successive catalytic water-gas shifting and CO2 in-situ adsorption separation processes and enhanced water-gas shifting for heat and mass transfer, a high-purity hydrogen product can be continuously prepared by the synthesis gas from the circulating fluidized bed at 450-600 DEG C.

Description

technical field [0001] The invention relates to a kind of calcium spraying circulating fluidized bed combustion gasification CO in a heavy oil residue furnace 2 In-situ adsorption enhanced water-vapor shift hydrogen production process, more specifically, is a special use of heavy oil residue as raw material, partial combustion of circulating fluidized bed, gasification, calcium spraying and desulfurization in the furnace to generate synthesis gas, and the synthesis gas is coupled CO 2 In-situ adsorption strengthens the water-vapor shift reaction and continuously produces high-purity hydrogen at normal pressure and (450-600) °C temperature range. Background technique [0002] The heavy oil residue comes from the catalytic oil gas production unit. It is a light and heavy mixed residual oil obtained after catalytic cracking of heavy oil. The main element is carbon, and the rest are hydrogen, oxygen, nitrogen, sulfur and other impurity elements. Heavy oil residue gasification ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B3/32
CPCY02P20/584
Inventor 豆斌林宋永臣蒋博张川杨明军王凯强
Owner DALIAN UNIV OF TECH
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