CN112827432A - Sulfuric acid decomposition tube with non-uniformly distributed catalyst bed added with reflux multi-tube and threaded outer wall surface - Google Patents
Sulfuric acid decomposition tube with non-uniformly distributed catalyst bed added with reflux multi-tube and threaded outer wall surface Download PDFInfo
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- CN112827432A CN112827432A CN202110020956.8A CN202110020956A CN112827432A CN 112827432 A CN112827432 A CN 112827432A CN 202110020956 A CN202110020956 A CN 202110020956A CN 112827432 A CN112827432 A CN 112827432A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a sulfuric acid decomposition tube with a backflow multi-tube and a threaded outer wall surface for a catalyst bed with uneven distribution. The sulfuric acid decomposition tube is made of silicon carbide, the outer wall surface of the sulfuric acid decomposition tube is in contact with high-temperature helium gas, the external threads on the surface of the outer wall surface of the sulfuric acid decomposition tube can play a role in strengthening heat exchange, and the three inner tubes provide good media for countercurrent heat exchange of heated sulfuric acid and a high-temperature gas mixture which returns back to flow. Meanwhile, the limited space is fully utilized through the arrangement of particles with different porosities in the catalyst area, the utilization rate of the catalyst is improved, and the processing cost is reduced. The invention mainly carries out structural design from the waste heat recovery effect of the inner tubes and the decomposition reaction of the catalytic area, the reflux design of the three inner tubes can strengthen heat exchange and reduce heat loss, the uneven catalyst particle arrangement can ensure that the decomposition is carried out efficiently at the upstream of the catalytic area, and the pressure drop resistance is reduced at the downstream of the catalyst, thereby reducing the cost. The sulfuric acid decomposition pipe provides reference for the design and manufacture of the actual sulfuric acid decomposition reactor of engineering.
Description
Technical Field
The invention relates to a sulfuric acid decomposition tube with a non-uniformly distributed catalyst bed, a reflux multi-tube and a threaded outer wall surface, and belongs to the field of nuclear reactor engineering and process heat utilization.
Background
Hydrogen is a clean and efficient energy carrier, which can play a positive role in relieving the world energy crisis. There are many methods for producing hydrogen, such as water electrolysis, coal gasification, and biological fermentation, but the hydrogen has wide application in the industrial field and the demand for hydrogen is large, so a large-scale hydrogen production method is required to provide a great demand for the future hydrogen industry chain. The hydrogen production process with the high-temperature gas cooled reactor coupled with the thermochemical iodine-sulfur cycle can greatly improve the hydrogen yield, has the advantage of saving electric energy compared with the traditional electrolytic water, has the advantage of cleanness, environmental protection and sustainability compared with coal gasification, and has important significance in the aspect of the engineering practical application of nuclear energy hydrogen production.
In the iodine-sulfur circulation hydrogen production process, the decomposition reaction of sulfuric acid needs to be carried out at high temperature, and the sulfuric acid has strong corrosivity, so that the efficient completion of the link is the key of the whole circulation, and therefore a sulfuric acid decomposition tube with a compact structure and reasonable layout needs to be provided to improve the decomposition rate.
Disclosure of Invention
The invention aims to provide a sulfuric acid decomposition tube with a non-uniformly distributed catalyst bed, a plurality of reflux pipes and a threaded outer wall surface, which can strengthen heat exchange between working media and improve the proceeding degree of sulfuric acid decomposition reaction, thereby providing reference for the engineering design of a sulfuric acid decomposer.
The sulfuric acid decomposition tube with the backflow multi-tube and the threaded outer wall surface for the catalyst bed with uneven distribution comprises a sulfuric acid decomposition tube;
one end of the sulfuric acid decomposition tube is opened;
at least two backflow inner pipes are arranged in the sulfuric acid decomposition pipe, gaps are arranged between the backflow inner pipes and the sulfuric acid decomposition pipe, and therefore annular cavities are formed between the backflow inner pipes and the sulfuric acid decomposition pipe;
a catalytic zone is arranged in the sulfuric acid decomposition tube far away from the open end of the sulfuric acid decomposition tube.
In the sulfuric acid decomposition tube, three reflux inner tubes are preferably arranged in the sulfuric acid decomposition tube;
and three backflow inner pipes are arranged in the sulfuric acid decomposition pipe at equal intervals.
In the sulfuric acid decomposition tube, along the direction from the opening end to the closed end of the sulfuric acid decomposition tube, the porosity of the catalyst in the catalytic zone is increased from small to large;
preferably, two catalytic zones with different porosities are arranged in the sulfuric acid decomposition tube, and a low-porosity catalytic zone and a high-porosity catalytic zone are sequentially arranged along the direction from the opening end to the closing end of the sulfuric acid decomposition tube, wherein the porosity of the catalyst in the low-porosity catalytic zone is smaller than that of the catalyst in the high-porosity catalytic zone;
namely, the low-porosity catalytic zone is positioned at the upstream of the catalyst bed, the decomposition rate of the sulfuric acid in the low-porosity catalytic zone is higher, and the high-efficiency decomposition of the sulfuric acid can be ensured by adopting denser catalyst arrangement;
the high porosity catalysis zone is positioned at the downstream of the catalyst bed, the decomposition rate of sulfuric acid in the high porosity catalysis zone tends to be gentle, the flow pressure drop loss can be reduced by adopting relatively sparse catalyst arrangement under the condition of less influence on the decomposition of the sulfuric acid, and meanwhile, the processing cost can be reduced by adopting relatively large catalyst particles, so that the economical efficiency is improved.
In the sulfuric acid decomposition tube, the outer wall surface of the sulfuric acid decomposition tube is provided with external threads, and heat exchange is enhanced through the structure;
the external thread is formed by extrusion molding or lathe machining.
In the sulfuric acid decomposition tube, the sulfuric acid decomposition tube is made of silicon carbide material, and the high-temperature helium and the sulfuric acid perform countercurrent heat exchange through the wall surface of the silicon carbide material;
the reflux inner tube is made of silicon carbide materials, and the heated sulfuric acid and the high-temperature gas mixture which is turned back are subjected to countercurrent heat exchange through the reflux inner tube, so that waste heat is effectively recovered, and the decomposition rate of the sulfuric acid is improved.
The working process of the sulfuric acid decomposition tube with the unevenly distributed catalyst bed and the reflux multi-tube is as follows:
sulfuric acid at normal temperature enters from an annular area between the sulfuric acid decomposition pipe and the backflow inner pipe and performs countercurrent heat exchange with external helium, and the thread structure on the outer wall surface has the functions of destroying a thermal boundary layer and strengthening heat exchange, so that the temperature of the sulfuric acid can be promoted to be increased; then, the sulfuric acid gradually heats up and changes phase, and enters a catalytic zone to generate decomposition reaction. Gaseous sulfuric acid firstly enters a low-porosity catalytic zone, the decomposition reaction of the sulfuric acid is violent in the zone, the decomposition rate is high, and therefore a flow zone with a high decomposition rate can be fully utilized through compact catalyst arrangement; then, the working medium enters the high-porosity catalytic zone, and the decomposition rate of the sulfuric acid is reduced and gradually tends to be gentle in the high-porosity catalytic zone, so that the cost performance is higher through the catalyst with larger particle size, and the decomposition rate and the pressure loss are comprehensively balanced. The gas mixture generated after decomposition comprises sulfur dioxide and oxygen, wherein gaseous sulfuric acid and sulfur trioxide which are not completely reacted are mixed, and are baffled at the bottom to enter the three backflow inner tubes together, and countercurrent heat exchange is formed between the gas mixture and the sulfuric acid in the annular space, so that waste heat recovery of the gas mixture can be realized.
The invention has the following beneficial effects:
1. the external thread structure on the sulfuric acid decomposition tube can strengthen the heat exchange between helium and sulfuric acid.
2. The catalyst arrangement with different uniformity degrees according to the change of the decomposition rate can make full use of the limited space of the catalytic zone, thereby not only ensuring the high-efficiency decomposition, but also reducing the pressure drop loss.
3. The arrangement of the three backflow inner pipes can recover waste heat, reduce heat loss, and still promote the decomposition of sulfuric acid by recovering heat.
Drawings
FIG. 1 is a schematic view of the structure of a sulfuric acid decomposition tube according to the present invention.
FIG. 2 is a schematic structural view of a transverse section of a sulfuric acid decomposition tube according to the present invention.
FIG. 3 is a schematic structural view of a longitudinal section of a sulfuric acid decomposition tube according to the present invention.
The respective symbols in the figure are as follows:
1 sulfuric acid decomposition tube, 2 external threads, 3 reflux inner tubes, 4 low porosity catalytic zones and 5 high porosity catalytic zones.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to the following embodiments.
As shown in FIG. 1, the sulfuric acid decomposition tube for adding a plurality of reflux multi-tubes and a screw thread outer wall surface to a catalyst bed with uneven distribution provided by the present invention comprises a sulfuric acid decomposition tube 1 having one end opened and the other end closed. Three backflow inner pipes 3 are arranged in the sulfuric acid decomposition pipe 1, the three backflow inner pipes 1 are arranged at equal intervals, and intervals are arranged between the backflow inner pipes 1 and the sulfuric acid decomposition pipe 1, and as shown in fig. 2, annular cavities are formed between the backflow inner pipes 3 and between the backflow inner pipes and the sulfuric acid decomposition pipe 1. The downstream of the sulfuric acid decomposition tube 1 is a catalytic zone, specifically, two catalytic zones with different porosities are arranged, and a low porosity catalytic zone 4 and a high porosity catalytic zone 5 are sequentially arranged along the direction from the opening end to the closed end of the sulfuric acid decomposition tube 1, namely, the low porosity catalytic zone 4 is positioned at the upstream of a catalyst bed, the decomposition rate of sulfuric acid in the zone is high, and the high-efficiency decomposition of the sulfuric acid can be ensured by adopting the dense catalyst arrangement; the high porosity catalytic zone 5 is located at the downstream of the catalyst bed, the decomposition rate of sulfuric acid in the high porosity catalytic zone tends to be gentle, the flow pressure drop loss can be reduced by adopting relatively sparse catalyst arrangement under the condition of less influence on the decomposition of sulfuric acid, and meanwhile, the processing cost can be reduced by adopting relatively large catalyst particles, and the economical efficiency is improved.
In order to enhance the heat exchange, an external thread 2 is disposed on the outer wall surface of the sulfuric acid decomposition tube 1, and as shown in fig. 1 and 3, the external thread 2 is formed by extrusion molding or lathe machining.
In the invention, the sulfuric acid decomposition tube 1 is made of silicon carbide material, and the high-temperature helium gas and the sulfuric acid perform countercurrent heat exchange through the wall surface of the silicon carbide material.
In the invention, the reflux inner tube 3 is made of silicon carbide material, and the heated sulfuric acid and the high-temperature gas mixture which is turned back are subjected to countercurrent heat exchange through the reflux inner tube 3, so that the waste heat is effectively recovered, and the decomposition rate of the sulfuric acid is improved.
As shown in FIG. 3, under normal conditions, the working flow of the sulfuric acid decomposition tube of the present invention is as follows:
1) the normal temperature sulfuric acid enters from the annular part of the sulfuric acid decomposition tube 1, exchanges heat with helium, gradually heats up and changes phase, and generates sulfur trioxide and water;
2) before reaching the catalytic zone, the sulfuric acid is basically decomposed to generate a mixture of sulfur trioxide and water, and the sulfur trioxide violently reacts in the low-porosity catalytic zone to generate sulfur dioxide and oxygen;
3) after sulfur trioxide passes through the low-porosity catalytic zone 4, the sulfur trioxide immediately enters the high-porosity catalytic zone 5, the decomposition rate is reduced, the pressure loss is reduced, and partial sulfur dioxide and oxygen are still generated;
4) the undecomposed sulfuric acid and sulfur trioxide and the generated mixture of sulfur dioxide, oxygen and water are converged at the bottom of the decomposition tube and enter the reflux inner tube 3 after baffling;
5) the gas mixture continuously carries out countercurrent heat exchange with the sulfuric acid in the annular area in the backflow inner pipe 3, the purpose of waste heat recovery is achieved, and finally the gas mixture flows out of the decomposition pipe to complete the sulfuric acid decomposition process.
The invention provides a design reference for the design of the sulfuric acid decomposition tube, if necessary, the non-uniform catalytic zone can be divided more finely, the non-uniform catalytic zone is not limited to be divided into two zones with high and low porosity, and the number of the backflow inner tubes can be changed to adapt to the actual engineering.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations.
Claims (8)
1. A sulfuric acid decomposition tube with a non-uniform distribution catalyst bed added with a reflux multi-tube and a thread outer wall surface comprises a sulfuric acid decomposition tube;
one end of the sulfuric acid decomposition tube is opened;
at least two backflow inner pipes are arranged in the sulfuric acid decomposition pipe, and gaps are arranged between the backflow inner pipes and the sulfuric acid decomposition pipe;
a catalytic zone is arranged in the sulfuric acid decomposition tube far away from the open end of the sulfuric acid decomposition tube.
2. The sulfuric acid decomposition tube of claim 1, wherein: and three backflow inner pipes are arranged in the sulfuric acid decomposition pipe.
3. The sulfuric acid decomposition tube of claim 2, wherein: and three backflow inner pipes are arranged in the sulfuric acid decomposition pipe at equal intervals.
4. The sulfuric acid decomposition tube according to any one of claims 1-3, wherein: along the direction from the opening end to the closed end of the sulfuric acid decomposition pipe, the porosity of the catalyst in the catalytic zone is increased from small to large.
5. The sulfuric acid decomposition tube of claim 4, wherein: the catalytic zone comprises a low-porosity catalytic zone and a high-porosity catalytic zone along the direction from the opening end to the closing end of the sulfuric acid decomposition tube, and the porosity of the catalyst in the low-porosity catalytic zone is smaller than that of the catalyst in the high-porosity catalytic zone.
6. The sulfuric acid decomposition tube according to any one of claims 1-5, wherein: and external threads are arranged on the outer wall surface of the sulfuric acid decomposition tube to achieve a heat exchange effect.
7. The sulfuric acid decomposition tube of claim 6, wherein: the external thread is formed by extrusion molding or lathe machining.
8. The sulfuric acid decomposition tube according to any one of claims 1-6, wherein: the sulfuric acid decomposition pipe is made of silicon carbide material;
the backflow inner pipe is made of silicon carbide materials.
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