CN115228388A - Heat pipe-tube type fixed bed propane dehydrogenation reactor with hydrogen separation mechanism - Google Patents
Heat pipe-tube type fixed bed propane dehydrogenation reactor with hydrogen separation mechanism Download PDFInfo
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- CN115228388A CN115228388A CN202210858166.1A CN202210858166A CN115228388A CN 115228388 A CN115228388 A CN 115228388A CN 202210858166 A CN202210858166 A CN 202210858166A CN 115228388 A CN115228388 A CN 115228388A
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 61
- 239000001294 propane Substances 0.000 title claims abstract description 42
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000000926 separation method Methods 0.000 title claims abstract description 27
- 230000007246 mechanism Effects 0.000 title claims abstract description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 156
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 32
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 12
- 238000010926 purge Methods 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005192 partition Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
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- 238000013461 design Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 101150058765 BACE1 gene Proteins 0.000 description 1
- 229910003414 BaCe0.9Y0.1O3−δ Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
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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
- 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
-
- 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
- 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a heat pipe-shell and tube fixed bed propane dehydrogenation reactor with a hydrogen separation mechanism, which comprises a reactor body, a plurality of reaction pipes and a plurality of heat pipes, wherein the heat pipes are arranged in the reactor body; the reactor body is internally provided with a horizontal partition plate, an upper tube plate and a lower tube plate, and the upper tube plate and the lower tube plate divide the reactor into a heating pool, a feeding area, a reaction area and a discharging area from bottom to top; the reactor body is provided with a reactant inlet communicated with the feeding zone, a purge gas inlet and a hydrogen outlet communicated with the reaction zone, and a product outlet communicated with the discharging zone; the reaction tubes are vertically arranged on the upper tube plate and the lower tube plate at intervals, the lower ends of the reaction tubes are communicated with the feeding area, and the upper ends of the reaction tubes are communicated with the discharging area; the middle part of each reaction tube penetrates through a heat pipe, and a catalyst bed layer is filled between the inner wall of each reaction tube and the outer wall of each heat pipe; the two ends of the heat pipe are closed, and a phase change medium is filled in the heat pipe; the lower end of the heat pipe extends into the heating pool. The invention has the beneficial effects that: the reaction zone of the reactor is provided with three independent closed spaces so as to meet the requirements of material exchange of a reaction side, a hydrogen removal side and a heat supply side, wherein the reaction side and the hydrogen removal side are respectively used for reaction and hydrogen removal, and the closed independent space of the heat supply side is used for heat supply.
Description
Technical Field
The invention relates to a reactor, in particular to a heat pipe-shell and tube fixed bed propane dehydrogenation reactor with a hydrogen separation mechanism.
Background
The light hydrocarbon dehydrogenation reaction system is a typical gas-solid phase reaction system, the commonly used catalyst is a metal catalyst or a molecular sieve catalyst with an acid center, and the catalytic reaction system generally adopts a fixed bed reactor and a fluidized bed reactor. Propane is a main component of petroleum associated gas, is abundant in reserves, but is mainly used as a gas fuel and a raw material for reforming synthesis gas at present due to relative stable molecular structure. If propane is subjected to catalytic dehydrogenation, propylene and hydrogen can be obtained simultaneously, two important industrial raw materials can be obtained simultaneously, and the economic added value of propane utilization can be improved remarkably. The reaction equation for propane dehydrogenation is shown below:
C 3 H 8 ＝C 3 H 6 +H 2 ΔH 0 ＝129.4kJ/mol,ΔG 0 ＝100.4kJ/mol
analysis from the thermodynamics shows that propane dehydrogenation is a typical endothermic reaction, and thermodynamic calculation results show that the process is limited by thermodynamics and the equilibrium conversion rate is low. Referring now to FIG. 1, which shows equilibrium conversions at different reaction temperatures at atmospheric pressure, it can be seen that the thermodynamic equilibrium conversion of propane is less than 30% in the usual reaction temperature range (450-650 ℃). This means that with a conventional reactor, both the single pass and the overall conversion are low. In order to improve the overall conversion rate of propane, after single-pass conversion, products and unreacted propane are discharged from a reaction system, hydrogen and propylene are separated out after processes such as cooling separation and the like,then sending the unconverted propane into the reactor for dehydrogenation reaction. The energy consumption (high temperature and high pressure) required for the wide range of temperature changes and gas separation in this process is very high, leading to an increase in production costs and more CO 2 And (4) discharging.
From the perspective of reaction engineering, if hydrogen can be removed from the reactor simultaneously with the reaction, changing the thermodynamic limitation on the reaction depth, the conversion of propane can be increased to a higher level, thereby reducing the cycle and downstream separation requirements and avoiding the high energy consumption and high carbon rejection in the above separation cycle design. And one of the products of the catalytic dehydrogenation of propane is separated and treated in real time by a membrane separation technology, so that the equilibrium conversion rate of the reaction can be changed, and the high conversion rate of the propane dehydrogenation reaction in a reactor is realized.
The proton membrane separation is a technology developed in recent years for hydrogen separation, and after a tubular proton membrane is introduced into a reaction system, the membrane reactor can realize reaction and H simultaneous reaction 2 The reactor was removed in real time to drive up the conversion of the feedstock. However, with the introduction of a tubular proton membrane, both sides of the membrane are occupied by process material, which means that the two separate enclosed spaces originally present in the fixed bed reactor are occupied by reaction material, and the enclosed space originally used for heat exchange will no longer be present, which presents a great challenge to the design of the reactor.
In fixed bed reactors, such as tubular fixed bed reactors capable of isothermal operation, the configuration of the reactor dictates that the reactor can generally provide only two separate enclosures, one for the reaction side (for catalyst loading and reactant passage) and the other for the utility side (for removal of heat of reaction in an exothermic reaction system and for supply of heat for endothermic reaction in an endothermic reaction system). On-line removal of H when it is desired to introduce a proton membrane into the reactor 2 In the process, two independent closed spaces need to be provided for the reaction side in the reactor, and three independent spaces are formed together with a public engineering side (heat supply or heat removal), and the three closed spaces need to exchange substances with the outside respectively. This adds significant difficulty and cost to both the reactor design and construction.
Current publications on proton membrane reactors ignore this problem. In the conventional proton membrane dehydrogenation reactor, one side of the tubular membrane is a reaction channel filled with a catalyst, and the other side of the tubular membrane is a channel for separated hydrogen, and some documents also show a heating process in the reaction tube, but in practice, the common design cannot accommodate two reaction side channels which are simultaneously present and a common engineering side channel which provides heat for the reaction.
When the two independent closed spaces are occupied by the reaction side and the hydrogen separation side, an additional independent closed space for providing the endothermic reaction heat required for the dehydrogenation reaction is created in the construction of the reactor. The heat supply pipes can be added in the geometric center of the reaction pipes, after the heat supply pipes in the reaction pipes are gathered, collectors of heat exchange media are built above and below the reaction pipes, and then the heat exchange media are sent out of the reactor, so that the purpose of circulating heat supply is achieved. However, the direct consequence of this design is that the reactor cannot be filled or replaced with catalyst, since the heat supply needs to be achieved by continuously feeding and removing the heat exchange medium into and from the reactor, and the continuous removal or feeding of heat from or to the reactor by the heat exchange medium is a common and standard method of engineering practice. In order to avoid the arrangement of internal parts such as a heat collector and the like, heat removal or heat supply is realized without depending on the exchange of heat exchange media.
Disclosure of Invention
The invention aims to provide a heat pipe-shell and tube fixed bed propane dehydrogenation reactor with a hydrogen separation mechanism aiming at the defects of the prior art.
The technical scheme adopted by the invention is as follows: a heat pipe-shell and tube fixed bed propane dehydrogenation reactor with a hydrogen separation mechanism comprises a reactor body, a plurality of reaction pipes and a plurality of heat pipes; the reactor body is internally provided with a horizontal clapboard, an upper tube plate and a lower tube plate, and the upper tube plate and the lower tube plate divide the reactor into a heating pool, a feeding area, a reaction area and a discharging area from bottom to top; the reactor body is provided with a reactant inlet communicated with the feeding zone, a purge gas inlet and a hydrogen outlet communicated with the reaction zone, and a product outlet communicated with the discharging zone; the reaction tubes are vertically arranged on the upper tube plate and the lower tube plate at intervals, the lower ends of the reaction tubes are communicated with the feeding area, and the upper ends of the reaction tubes are communicated with the discharging area; the middle part of each reaction tube penetrates through a heat pipe, and a catalyst bed layer is filled between the inner wall of each reaction tube and the outer wall of each heat pipe; the two ends of the heat pipe are closed, and a phase change medium is filled in the heat pipe; the lower end of the heat pipe extends into the heating pool.
According to the scheme, the reaction tube is made of a proton membrane through which hydrogen can pass, and the proton membrane is made of a metal-ceramic two-phase proton conduction membrane material or a ceramic-ceramic two-phase proton conduction membrane material.
According to the scheme, the heat pipe comprises an upper heat pipe section and a lower heat pipe section, wherein the upper heat pipe section is positioned in the reaction pipe and extends to the top of the reaction pipe; the lower section of the heat pipe is positioned in the feeding area and the heating pool; length of the lower section of the heat pipe is 1/5-1/3 of the length of the upper section of the heat pipe.
According to the scheme, the whole heat pipe is cylindrical, and the inner surface of the heat pipe is provided with the toothed flow guide groove.
According to the scheme, the phase change medium filled in the heat pipe is liquid metal Na or K.
According to the scheme, the catalyst bed layer is made of a chromium catalyst or a platinum catalyst.
According to the scheme, the reaction tubes are arranged in the reactor body at intervals in a staggered manner; the reaction tube is coaxial with the heat pipe inside the reaction tube.
According to the scheme, the reactant inlet is provided with the feeding distributor, and the feeding distributor is positioned in the feeding area.
According to the scheme, the reactor body is provided with a nitrogen inlet and a nitrogen outlet which are communicated with the heating pool.
According to the scheme, the reactor body comprises a cylindrical shell, a lower end enclosure fixed at the bottom of the shell and an upper end enclosure fixed at the top of the shell.
According to the scheme, the hydrogen outlet is connected with a negative pressure air pump through a pipeline; the purge gas inlet is in communication with an inert gas supply conduit.
The invention has the beneficial effects that:
1. the reaction zone of the reactor is provided with three independent closed spaces so as to meet the requirements of material exchange of a reaction side, a hydrogen removal side and a heat supply side, wherein the reaction side and the hydrogen removal side are respectively used for reaction and hydrogen removal, and the closed independent space of the heat supply side is used for heat supply.
2. The reaction tube is made of a metal-ceramic two-phase proton conduction membrane or a ceramic-ceramic two-phase proton conduction membrane, the catalyst is filled in the reaction tube, hydrogen generated by propane dehydrogenation can be separated in real time during reaction, the reaction and the separation are coupled, the limitation of the thermal conversion depth in the reaction process is broken through, the equilibrium conversion rate of the propane dehydrogenation reaction is improved, the single-pass conversion rate of propane is promoted, meanwhile, the side reaction can be inhibited along with the effective removal of hydrogen, and the selectivity of the hydrogen is further improved.
3. The heat pipe is arranged in the reaction pipe, so that the continuous heat supply to the reactor can be realized under the condition of not additionally increasing a heat exchange medium: the heat pipe adopts external independent heating to ensure that a liquid section in the heat pipe absorbs heat to achieve vaporization, a gas phase substance axially rises after steam pressure is increased, and gas condenses to release heat after reaching a condensation section of the heat pipe to continuously supply heat for a catalyst bed layer, so that the reaction energy required after the reaction depth is improved is met, meanwhile, the near-isothermal reaction condition in the reactor pipe is realized, the reaction dynamics behavior is optimized, and the selectivity of a target product is further improved.
Drawings
FIG. 1 is a graph showing the relationship between the temperature of the dehydrogenation reaction of propane and the equilibrium conversion.
Fig. 2 is an appearance diagram of an embodiment of the present invention.
FIG. 3 is a sectional view of the inside of a reactor according to an embodiment of the present invention.
FIG. 4 is a sectional view of a single reaction tube inside a reactor which does not show one embodiment of the present invention
Fig. 5 is an axial sectional view of the heat pipe.
FIG. 6 is a schematic cross-sectional view of a heat pipe.
FIG. 7 is a schematic view showing the arrangement of reaction tubes in the reactor body.
FIG. 8 is a schematic diagram of the arrangement of the reaction tube and the heat pipe.
Wherein: 1-lower end enclosure; 2-the lower section of the heat pipe; 3-a reactant inlet; 4-a shell; 5-a reaction tube; 6-a hydrogen outlet; 7, sealing the head; 8-product outlet; 9-catalyst bed layer; 10-upper section of heat pipe; 11-purge gas inlet; 12-a feed distributor; 13-lower tube sheet; 14-upper tube sheet; 15-nitrogen inlet; 16-nitrogen outlet; 17-a heating pool; 18-a flow guide groove; 19-a separator.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
As shown in fig. 2, the heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism comprises a reactor body, a plurality of reaction pipes 5 and a plurality of heat pipes; a horizontal partition plate 19, an upper tube plate 14 and a lower tube plate 13 are arranged in the reactor body, and the upper tube plate and the lower tube plate 13 divide the reactor into a heating pool 17, a feeding area, a reaction area and a discharging area from bottom to top; the reactor body is provided with a reactant inlet 3 communicated with the feeding area, a purge gas inlet 11 and a hydrogen outlet 6 communicated with the reaction area, and a product outlet 8 communicated with the discharging area; the reaction tubes 5 are vertically arranged on the upper tube plate 13 and the lower tube plate 13 at intervals, the lower ends of the reaction tubes 5 are communicated with the feeding area, and the upper ends of the reaction tubes 5 are communicated with the discharging area; a heat pipe penetrates through the middle part of each reaction pipe 5, and a catalyst bed layer 9 is filled between the inner wall of each reaction pipe 5 and the outer wall of each heat pipe; the two ends of the heat pipe are closed, and a phase change medium is filled in the heat pipe; the lower end of the heat pipe extends into the heating bath 17.
In the invention, 3 independent areas are separated in a reaction area, wherein a shell side is arranged between the outer wall of a reaction tube 5 and the inner wall of a reactor body and is used for removing hydrogen separated from the reaction tube 5; a tube side is arranged between the inner wall of the reaction tube 5 and the outer wall of the heat pipe, and the tube side is filled with a catalyst and used for propane dehydrogenation reaction; the heat pipe in the reaction tube 5 is the heat supply side and provides heat for the reaction.
Preferably, the reaction tube 5 is made of a proton membrane which can be penetrated by hydrogen, and the proton membrane is made of a metal-ceramic two-phase proton conducting membrane material or a ceramic-ceramic two-phase proton conducting membrane material. The reaction tube 5 constructed by the proton conducting membrane removes hydrogen, one of reaction products, in real time on line by means of membrane separation while the propane dehydrogenation reaction is carried out, and the hydrogen enters the shell side of the reactor from the tube side through the proton conducting membrane.
Preferably, the hydrogen outlet 6 is connected with a negative pressure air pump through a pipeline. The purge gas inlet 11 is in communication with an inert gas supply conduit. In the invention, on the shell side of the reactor, hydrogen is exhausted in a mode of vacuum pumping to form negative pressure or is exhausted by inert gas purging.
Preferably, the heat pipe comprises a heat pipe upper section 10 and a heat pipe lower section 2, wherein the heat pipe upper section 10 is located in the reaction tube 5 and extends to the top of the reaction tube 5; the lower section 2 of the heat pipe is positioned in the feeding area and the heating pool 17; length of the lower section 2 of the heat pipe 1/5-1/3, preferably 1/4-1/3, of the length of the upper section 10 of the heat pipe.
Preferably, the whole heat pipe is cylindrical, the inner surface of the heat pipe is provided with a toothed flow guide groove 18, and the flow guide groove 18 increases the heat exchange area when liquid flows downwards under the action of gravity.
Preferably, the phase change medium filled in the heat pipe is liquid metal Na or K. Heat is supplied to the catalyst bed layer 9 through a heat pipe sealed by phase-change fluid, so as to maintain the temperature of the catalyst bed layer 9 and promote the reaction.
Preferably, the catalyst of the propane dehydrogenation reaction system is a chromium-based catalyst or a platinum-based catalyst.
Preferably, the reaction tubes 5 are arranged in the reactor body at intervals in a staggered manner, that is, the reaction tubes 5 in two adjacent columns/rows are arranged in a staggered manner; the reaction tube 5 is coaxial with the heat pipe inside it, as shown in fig. 7 and 8.
Preferably, the reactant inlet 3 is fitted with a feed distributor 12, the feed distributor 12 being located within the feed zone.
Preferably, the reactor body comprises a cylindrical shell 4, a lower head 1 fixed at the bottom of the shell 4, and an upper head 7 fixed at the top of the shell 4.
Preferably, the reactor body is provided with a nitrogen inlet 15 and a nitrogen outlet 16 which are communicated with a heating pool 17, and the high-temperature nitrogen improves the heat required by the phase change of the phase-change fluid in the heat pipe.
The heat pipe is a two-phase heat transfer device working isothermally, the appearance is generally a totally closed metal pipe, distribute the core of different structures on its inner surface, is filled with the phase-change fluid inside the pipe, the choice of the phase-change fluid is correlated with reaction side reaction temperature. When the temperature of the phase-change fluid is matched with the working temperature of the catalyst in the bed layer of the reactor, the phase-change fluid is subjected to phase change to reach vapor-liquid balance, liquid is positioned at one end of the heat pipe, gas is positioned at the other end of the heat pipe, and vaporization and condensation are respectively carried out at two ends of the heat pipe. The liquid end in the heat pipe absorbs heat to be vaporized, the steam pressure is increased, the gas phase substance rises along the axial direction, the gas reaches the condensing section to be condensed to give out heat for the liquid, heat is provided for the reaction side (reactant and product), the heat required by reaction heat absorption is compensated, the reaction temperature is maintained, the conversion rate of the reactant is improved, and then the liquid flows to the liquid side along the core under the action of capillary force. The externally heated heat pipe starts to work, the raw material gas absorbs heat under the action of the heat pipe to react, and the reaction temperature is 550-600 ℃. The metal liquid at the lower part of the heat pipe is heated and vaporized into gas, the gas rises and reaches the condensing section of the heat pipe to release heat and then flows back to the lower part of the heat pipe, and the process is repeated in a circulating way.
The heat pipe is a pressure-resistant high-temperature-resistant closed pipe, and the selected material can be aluminum, silicon carbide and the like. The circularly operated heat pipe has a cylindrical external geometry and a toothed guide groove 18 on the internal surface, as shown in fig. 6, and this design can provide a flow channel for the phase-change material condensed into a liquid phase, and can also increase the heat exchange area and enhance the heat transfer. The phase change and flow of the phase change material in the heat pipe can be represented by the following figure 5, the liquid phase at the bottom rises along the cavity inside the heat pipe after being heated, heat is continuously released to the catalyst bed layer 9 through the flow guide groove 18 and the wall of the heat pipe in the rising process, the gas phase material forms condensation on the surface of the flow guide groove 18, and returns to the bottom of the heat pipe along the flow guide groove 18 under the action of capillary force. The input power of the heat pipe can be regulated and controlled through the temperature and the flow rate of the high-temperature nitrogen.
In the present invention, the inner diameter of the reaction tube 5 is 1 to 3 inches, preferably 1.5 to 2 inches. The tube length of the reaction tube 5 is 2 to 12m, preferably 6 to 12m. The reaction tubes 5 are arranged in an equilateral triangle in the reactor, and the tube pitch of the reaction tubes 5 is 1.2 to 1.3 times of the outer diameter of the tubes. The inner diameter of the heat pipe is preferably 1/4-3/4 inch; the upper section 10 of the heat pipe extends to the top of the reaction tube 5, and the length of the lower section 2 of the heat pipe is 1/5-1/3, preferably 1/4-1/3, of the length of the reaction tube 5.
In the invention, the actual size (including the outer diameter and the height) of the reactor, the number of the reaction tubes 5 and the number of the corresponding heat pipes are determined by the capacity and the catalyst activity which are required to be realized by the reactor. The pressure of the reaction side of the reactor (namely the inner side of the reaction tube 5) is 0.1-0.3 MPa, and the temperature is 550-650 ℃.
The reactor is used for producing propylene and hydrogen from propane through catalytic dehydrogenation reaction, and the specific working principle is as follows: raw material gas (namely propane) preheated to the reaction temperature outside the reactor enters a feeding area of the reactor from a reactant inlet, enters the reaction tube 5 from the lower end and rises in the reaction tube 5; high-temperature nitrogen or other media supply heat to the lower section 2 (evaporation section) of the heat pipe in the heating pool 17, the liquid phase change media in the heating heat pipe is gasified into gas, the gas rises to the upper section 10 (heat release condensation section) of the heat pipe to supply heat to the catalyst bed layer 9, the raw gas reacts, the condensed phase change media returns to the lower section 2 of the heat pipe under the action of gravity, and the process is repeated; the raw material gas reacts to generate propylene and hydrogen, the propylene is collected in a discharge area (namely an upper end enclosure 7) through the upper end of the reaction tube 5 and is discharged from a product outlet 8 at the top; hydrogen is separated by the reaction tube 5, enters the shell side between the reaction tube 5 and the reactor body, and is discharged in a vacuum pumping mode or is discharged by inert gas purging to reduce the hydrogen partial pressure in the shell side; the heat pipe in the reaction pipe 5 continuously supplies heat for dehydrogenation reaction, and high-temperature nitrogen or other media supply heat to the lower section 2 (evaporation section) of the heat pipe in the heating pool 17.
Example one
The height of the reactor is 10m, and the inner diameter is 4m; the proton membrane material adopted by the reaction tube 5 is a ceramic-ceramic two-phase proton conduction membrane，BaCe 0.85 Zr 0.20 Y 0.15 O 3-δ -Ce 0.85 Gd 0.15 O 2-δ (ii) a The length of the reaction tube 5 is 6m, the tube diameter is 1.5 inches, the tube diameter is 0.5 inches, the length of the lower section 2 of the heat tube is 1.5m, and the upper section 10 of the heat tube extends into the reaction tube 5 for heat supply; the catalyst bed 9 is 2.2wt% of PtIn 2 /Al 2 O 3 A catalyst.
Raw material gas propane enters a membrane reaction tube 5 from a reactant inlet 3 at the lower part of the reactor, the raw material gas is subjected to catalytic dehydrogenation reaction under the conditions that the temperature is 600 ℃ and the pressure is 0.1MPa to generate propylene and hydrogen, and under the action of purge gas, hydrogen of one of products is discharged from a hydrogen outlet 6 side after being permeated through the reaction tube 5 and is collected; propylene is discharged from the overhead product outlet 8 and collected.
The experiment calculation shows that the conversion rate of the propane is increased from 20% to 86%, and meanwhile, with the effective removal of hydrogen of one of the reaction products, the occurrence of side reaction can be inhibited, and the selectivity of the hydrogen is further improved.
Example two
The height of the reactor is 12m, and the inner diameter is 5m; the proton membrane material adopted by the reaction tube 5 is a ceramic-metal two-phase proton conduction membrane, baCe0.9Y 0.1 O 3-δ Ni (60; the length of the reaction tube 5 is 8m, and the diameter of the tube is 1.2 inches; the pipe diameter of the heat pipe is 0.4 inch, the length of the lower section 2 of the heat pipe is 2m, and the upper section 10 of the heat pipe extends into the reaction pipe 5 for heat supply; the catalyst bed layer 9 adopts 18wt% Cr-Al 2 O 3 A catalyst.
Raw material gas propane enters a membrane reaction tube 5 from a reactant inlet 3 at the lower part of the reactor, the raw material gas is subjected to catalytic dehydrogenation reaction at the temperature of 600 ℃ and the pressure of 0.1MPa to generate propylene and hydrogen, and under the action of purge gas, hydrogen of one of products is permeated through the reaction tube 5 and then discharged from a hydrogen outlet 6 side and collected; propylene is discharged from the overhead product outlet 8 and collected.
The experiment calculation shows that the conversion rate of the propane is improved from 20% to 83%, and meanwhile, with the effective removal of hydrogen of one of the reaction products, the occurrence of side reaction can be inhibited, and the selectivity of the hydrogen is further improved.
It should be noted that, although the present invention has been described in detail with reference to the embodiments, it will be apparent to those skilled in the art that modifications, equivalents, improvements and the like can be made in the embodiments or some of the features of the embodiments without departing from the spirit and the principle of the present invention.
Claims (10)
1. A heat pipe-shell and tube fixed bed propane dehydrogenation reactor with a hydrogen separation mechanism is characterized by comprising a reactor body, a plurality of reaction pipes and a plurality of heat pipes; the reactor body is internally provided with a horizontal clapboard, an upper tube plate and a lower tube plate, and the upper tube plate and the lower tube plate divide the reactor into a heating pool, a feeding area, a reaction area and a discharging area from bottom to top; the reactor body is provided with a reactant inlet communicated with the feeding zone, a purge gas inlet and a hydrogen outlet communicated with the reaction zone, and a product outlet communicated with the discharging zone; the reaction tubes are vertically arranged on the upper tube plate and the lower tube plate at intervals, the lower ends of the reaction tubes are communicated with the feeding area, and the upper ends of the reaction tubes are communicated with the discharging area; the middle part of each reaction tube penetrates through a heat pipe, and a catalyst bed layer is filled between the inner wall of each reaction tube and the outer wall of each heat pipe; the two ends of the heat pipe are closed, and a phase change medium is filled in the heat pipe; the lower end of the heat pipe extends into the heating pool.
2. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the reaction pipe is made of proton membrane which can pass through by hydrogen, and the proton membrane is made of metal-ceramic two-phase proton conducting membrane material or ceramic-ceramic two-phase proton conducting membrane material.
3. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the heat pipe comprises an upper heat pipe section and a lower heat pipe section, the upper heat pipe section is located inside the reaction tube and extends to the top of the reaction tube; the lower section of the heat pipe is positioned in the feeding area and the heating pool; length of the lower section of the heat pipe is 1/5-1/3 of the length of the upper section of the heat pipe.
4. A heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism as claimed in claim 1, wherein the heat pipe is cylindrical in whole and the inner surface of the heat pipe is provided with a toothed guiding groove.
5. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the phase change medium filled in the heat pipe is liquid metal Na or K.
6. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the catalyst bed is made of chromium-based catalyst or platinum-based catalyst.
Preferably, the reaction tubes are arranged in the reactor body at intervals in a staggered manner; the reaction tube is coaxial with the heat pipe inside the reaction tube.
7. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with a hydrogen separation mechanism according to claim 1, wherein the reactant inlet is equipped with a feed distributor, and the feed distributor is located in the feed zone.
8. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the reactor body is provided with a nitrogen inlet and a nitrogen outlet which are communicated with the heating pool.
9. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the reactor body comprises a cylindrical shell, a lower end socket fixed at the bottom of the shell, and an upper end socket fixed at the top of the shell.
10. The heat pipe-shell and tube fixed bed propane dehydrogenation reactor with hydrogen separation mechanism according to claim 1, wherein the hydrogen outlet is connected with a negative pressure air pump through a pipeline; the purge gas inlet is in communication with an inert gas supply conduit.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030068261A1 (en) * | 2001-08-02 | 2003-04-10 | Hassan Taheri | Flow reactors for chemical conversions with heterogeneous catalysts |
| JP2008081385A (en) * | 2006-09-29 | 2008-04-10 | Petroleum Energy Center | Method for producing hydrogen and reaction tube for it |
| CN201144199Y (en) * | 2007-10-12 | 2008-11-05 | 上海工程化学设计院有限公司 | Converter for chloroethylene synthesis |
| CN102574089A (en) * | 2009-10-19 | 2012-07-11 | 戴维加工技术有限公司 | Vessel for containing catalyst in a tubular reactor |
| CN103962065A (en) * | 2014-05-16 | 2014-08-06 | 赛鼎工程有限公司 | Shell and tube fixed-bed reactor |
| US20170274340A1 (en) * | 2016-03-24 | 2017-09-28 | Korea Institute Of Science And Technology | Shell-and-multi-double concentric-tube reactor and heat exchanger |
| CN215464287U (en) * | 2021-08-12 | 2022-01-11 | 成都市润和盛建石化工程技术有限公司 | Low-carbon alkane dehydrogenation tube array type fixed bed reactor |
-
2022
- 2022-07-20 CN CN202210858166.1A patent/CN115228388A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030068261A1 (en) * | 2001-08-02 | 2003-04-10 | Hassan Taheri | Flow reactors for chemical conversions with heterogeneous catalysts |
| JP2008081385A (en) * | 2006-09-29 | 2008-04-10 | Petroleum Energy Center | Method for producing hydrogen and reaction tube for it |
| CN201144199Y (en) * | 2007-10-12 | 2008-11-05 | 上海工程化学设计院有限公司 | Converter for chloroethylene synthesis |
| CN102574089A (en) * | 2009-10-19 | 2012-07-11 | 戴维加工技术有限公司 | Vessel for containing catalyst in a tubular reactor |
| CN103962065A (en) * | 2014-05-16 | 2014-08-06 | 赛鼎工程有限公司 | Shell and tube fixed-bed reactor |
| US20170274340A1 (en) * | 2016-03-24 | 2017-09-28 | Korea Institute Of Science And Technology | Shell-and-multi-double concentric-tube reactor and heat exchanger |
| CN215464287U (en) * | 2021-08-12 | 2022-01-11 | 成都市润和盛建石化工程技术有限公司 | Low-carbon alkane dehydrogenation tube array type fixed bed reactor |
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