Method and device for reprocessing CO;containing exhaust gases

• US 8,911,520 B2
• Filed: 12/18/2008
• Issued: 12/16/2014
• Est. Priority Date: 12/20/2007
• Status: Expired due to Fees

• Current Assignee: Ecoloop GmbH
• Original Assignee: Ecoloop GmbH
• Inventors: Mller, Roland
• Primary Examiner(s): Akram, Imran
• Application Number:
  US12/809,383
• Publication Number:
  US 20110094159A1
• Time in Patent Office: 2,189 Days
• US Class Current: 48/197.R
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 3/16 using catalysts
• CPC Class Codes: C10B 49/06 according to the moving bed type
• CPC Class Codes: C10J 2300/092 Wood, cellulose
• CPC Class Codes: C10J 2300/093 Coal
• CPC Class Codes: C10J 2300/0946 Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0969 Carbon dioxide
• CPC Class Codes: C10J 2300/0996 Calcium-containing inorganic materials, e.g. lime
• CPC Class Codes: C10J 2300/16 Integration of gasification processes with another plant or parts within the plant
• CPC Class Codes: C10J 2300/1807 Recycle loops, e.g. gas, solids, heating medium, water
• CPC Class Codes: C10J 3/14 using gaseous heat-carriers
• CPC Class Codes: C10J 3/66 by introducing them into the gasification zone
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02E 20/18 Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention relates to a method for reprocessing CO₂-containing exhaust gases in a multistage reduction process. The CO₂-containing exhaust gas is conducted in the counter stream to a solid mass stream of inert bulk material and organic material that can be thermally decomposed through a plurality of zones (4, 3, 2, 1) into a pressure equalization region and is thereby converted into pyrolysis gases. In the flow direction of the solid mass stream in a fuel gas production stage (1) at 250-700° C., the organic matter is thermally decomposed under reducing conditions into short-chained hydrocarbons, hydrogen and carbon monoxide to produce coke and residue. In an intermediate stage (2) with increasing temperature, oxidation of the pyrolysis coke is carried out, wherein the developing carbon monoxide is suctioned off counter to the solid mass stream in the direction of the fuel gas production stage (1). In a carbon monoxide production stage (3) at 800-1,600° C., the remaining coke residue is converted with carbon dioxide into carbon monoxide by setting the pressure and temperature according to the Boudouard equilibrium. In a cooling stage (4), the developing solid residual material and the bulk material are cooled in the CO₂ counter stream to below 100° C. and are separated, wherein the bulk material is returned to the cycle.

Claims

1. A method for reprocessing CO₂-containing exhaust gases in a multi-stage reduction process, the CO₂-containing waste gas being conducted in a solid mass flow of bulk material, which cannot be gasified, and a thermally decomposable organic mass, through a plurality of zones to produce pyrolysis gases, said method comprising:

a. thermally decomposing organic mass of a solid mass flow of bulk material under reducing conditions to form i) pyrolysis gases comprising short-chain hydrocarbons, hydrogen and carbon monoxide, along with ii) the creation of coke and a residue in a combustion gas generating stage;

b. performing oxidation of the coke in an intermediate stage at an increasing temperature, in which the carbon monoxide being created is drawn off opposite the direction of the solid mass flow in the direction of the combustion gas generating stage;

c. converting remaining coke residue, together with carbon dioxide, in a carbon monoxide generating stage at 800 to 1,600°

C. to carbon monoxide while adjusting the pressure and temperature in accordance with the Boudouard equilibrium;

d. cooling solid residue materials and coarse pieces of bulk material which was not gasified in a cooling stage in the CO₂ counterflow to below 100°

C. and are moved out; and

e. returning at least the removed bulk material which was not gasified into the circulation after having been taken out.

2. The method in accordance with claim 1, wherein in the intermediate stage a temperature of 600 to 1,000°

C. is set and the pressure is reduced, so that in this stage a pyrolysis of the organic mass and the Boudouard equilibrium reaction run simultaneously at low pressure and low temperature.

3. The method in accordance with claim 2, wherein the pyrolysis gases are removed by means of an aspirating device, which creates the underpressure in the intermediate stage.

4. The method in accordance with claim 1, wherein a mixture of coarse and fine bulk material is employed as a pressure reservoir in a pressure compensating zone above a combustion gas generating zone.

5. The method in accordance with claim 1, wherein a temperature and pressure control takes place by means of the composition of the solid masses and/or their throughput speed.

6. The method in accordance with claim 1, wherein a temperature and pressure control takes place by means of the ratio of the supplied, thermally-decomposable organic mass, and possibly added oxygen-containing gas, to CO₂ takes place.

7. The method in accordance with claim 1, wherein a carbon carrier is additionally admixed to the solid mass flow.

8. The method in accordance with claim 1, wherein water or steam is metered into the cooling stage, the intermediate stage or the carbon monoxide stage.

9. The method in accordance with claim 1, wherein the multi-stage reduction process is performed in a calcination shaft kiln furnace, in which the bulk material is conducted from the top to the bottom, so that the carbon-containing components are thermally split with extensive oxygen exclusion and with the creation of pyrolysis gases containing short-chain molecules of a chain length of <

C4, and the pyrolysis gases being generated are exhausted from the calcination kiln furnace.

10. The method in accordance with claim 9, wherein basic calcinates, their precursor stages, or inert bulk materials are employed as bulk materials, preferably in the form of quicklime (CaO).

11. The method in accordance with claim 1, wherein bulk material of a grain size in the range of 0.5 to 15 cm is removed from the cooling stage for return to the cycle.

12. The method in accordance with claim 11, wherein by means of a gas filtration the pyrolysis gases are cleaned of carried-along fine dust containing pyrolysis residue bonded to the fine bulk material particles.

13. The method in accordance with claim 1, wherein the pyrolysis gases are employed as synthesis gas for chemical processes and/or for thermal uses.

14. The method in accordance with claim 1, wherein the pyrolysis gases are separated into their gas components carbon monoxide, carbon dioxide, hydrogen and hydrocarbons by means of partial liquefaction and/or pressure change absorption.

15. The method in accordance with claim 14, wherein carbon monoxide is employed as the synthesis gas for use as a material in chemical processes.

16. The method in accordance with claim 14, wherein the separated hydrogen is employed as material for thermal and/or material purposes.

17. The method in accordance with claim 14, wherein the hydrocarbons are employed for thermal and/or material purposes and/or a fuels.

18. The method in accordance with claim 1, wherein by means of a water gas shift reaction through a catalyzed reaction below 500°

C. with water vapor, the pyrolysis gases are essentially converted into hydrogen and carbon dioxide, which are separated by means of physical separation methods, wherein hydrogen is employed for thermal and/or material uses, and the CO₂ being generated is partially returned for constituting the counterflow.

19. The method in accordance with claim 1, wherein the CO₂ waste gas to be reconstituted is generated in a combustion process by the use of fossil fuels, and the pyrolysis gases being created in the course of reconstitution are again employed in the combustion process.

20. The method in accordance with claim 1, wherein the CO₂-containing waste gas is generated in a calcination process, in which carbonates are converted into oxides by splitting them off from CO₂, in the course of which the pyrolysis gases being created during reconstitution are employed for providing a portion of the heat energy required for the calcination process.