CN117985652A - Organic hydride dehydrogenation reaction systems and methods - Google Patents
Organic hydride dehydrogenation reaction systems and methods Download PDFInfo
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- CN117985652A CN117985652A CN202211352071.9A CN202211352071A CN117985652A CN 117985652 A CN117985652 A CN 117985652A CN 202211352071 A CN202211352071 A CN 202211352071A CN 117985652 A CN117985652 A CN 117985652A
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- 150000004678 hydrides Chemical class 0.000 title claims abstract description 67
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims description 31
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052573 porcelain Inorganic materials 0.000 claims description 19
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 14
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000001924 cycloalkanes Chemical class 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 claims description 2
- OQXMLPWEDVZNPA-UHFFFAOYSA-N 1,2-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1C1CCCCC1 OQXMLPWEDVZNPA-UHFFFAOYSA-N 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
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- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
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- 238000009834 vaporization Methods 0.000 description 1
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses an organic hydride dehydrogenation reaction system and a method, belonging to the technical field of chemical technology, wherein the system comprises N-level tubular reactors with sequentially connected tube layers and sequentially connected shell layers, wherein N is more than or equal to 2; the heat carrier is divided into three strands, wherein two strands enter the shell layer of the nth-stage tubular reactor to provide heat for dehydrogenation reaction in the tube layer, and the technical scheme of cascade control of the flow of the third strand and the temperature of the outlet product of the tube layer of the nth-stage tubular reactor is adopted, so that the problems of catalyst coking deactivation and difficult steady-state operation caused by overhigh and uneven temperature of the reactor bed are well solved.
Description
Technical Field
The invention belongs to the field of chemical technology, and particularly relates to a dehydrogenation method, in particular to an organic hydride dehydrogenation reaction system and method.
Background
Hydrogen energy is a green sustainable new energy source with good application prospect, and hydrogen storage and transportation is a key difficulty in hydrogen energy application. In recent years, the liquid organic hydride hydrogen storage technology based on a chemical reaction method is attracting attention more and more due to the advantages of large hydrogen storage amount, high energy density, safe and convenient liquid storage and transportation and the like. By the method, hydrogen can be subjected to hydrogenation reaction with unsaturated hydrocarbon at a production place and converted into liquid organic hydride for transportation, and the organic hydride is subjected to dehydrogenation reaction at a hydrogen application place such as a hydrogenation station or a factory to obtain hydrogen and the unsaturated hydrocarbon, and then the unsaturated hydrocarbon is transported to the hydrogen production place.
The dehydrogenation reaction is a strong endothermic reaction, a large amount of heat is required to be provided from the outside during the reaction, and particularly for organic hydrides with high hydrogen density, the heat required for the reaction is higher, for example, the dehydrogenation heat of methylcyclohexane reaches 250kJ/mol, so that heat supply is critical to the dehydrogenation process, and in most of the known dehydrogenation processes and production devices, the heat required for the dehydrogenation reaction is brought into the reactor by the reaction raw materials before the reactor and a heat carrier entering the shell layer of the reactor. The temperature of the heat carrier is required to be higher than the temperature in the tube so as to provide heat for the reaction, but the catalyst is easy to coke and deactivate due to the high temperature, and at the inlet of the reactor, the reaction rate is high, the reaction absorbs a large amount of heat, the outside cannot supply heat in time, so that the system temperature is rapidly reduced, the reaction rate is reduced along with the progress of the reaction, the heat supply rate and the reaction rate maintain a relatively balanced state, and the system temperature is gradually increased at the moment, so that the catalyst is adversely affected by the increase of the system temperature after the decrease of the system temperature.
US20170015553A1 prevents carbon deposition on the dehydrogenation catalyst by recycling a portion of the hydrogen produced by the dehydrogenation reaction of the organic liquid, thereby inhibiting a decrease in catalyst activity. The specific method comprises the following steps: the hydrogen production system includes a first dehydrogenation unit for generating hydrogen by dehydrogenation of the organic liquid in the presence of a first catalyst, and a second dehydrogenation unit for receiving a product of the first dehydrogenation unit and generating hydrogen by dehydrogenation of the organic liquid remaining in the product in the presence of a second catalyst.
CN112707368A separates out hydrogen and unreacted products by cooling the reaction products of the first reactor and then feeding the reaction products into a gas phase separator, and then heating the unreacted products and feeding the unreacted products into a second reactor to perform dehydrogenation reaction, so that coking of the catalyst is avoided by a method of separating hydrogen.
CN215464287U discloses a low-carbon alkane dehydrogenation tube type fixed bed reactor, which provides heat for the dehydrogenation reaction in the tube through molten salt, so that the catalyst bed layer is in the optimal reaction zone, and the service time of the catalyst is prolonged.
The process heat carrier enters the tubular reactor at one position at a certain temperature and flow, so that the inlet temperature of the tubular layer and the outlet temperature of the tubular layer are difficult to adjust, the operation elasticity is small, and the reasonable conversion rate and the reaction rate of each section of reactor are difficult to ensure under the working conditions of uneven catalyst filling, partial inactivation of the catalyst and the like.
Disclosure of Invention
In order to solve the problems that the temperature of the reactor bed layer of the dehydrogenation process is too high and uneven, so that the catalyst is easy to coke and deactivate and difficult to operate in a steady state. The invention provides a tubular reactor system, a method for dehydrogenating organic hydride and application thereof, and has the advantages of long service life of a catalyst, high operation elasticity and stable operation.
On one hand, the invention provides an organic hydride dehydrogenation reaction system, which comprises N-level tubular reactors with sequentially connected tube layers and sequentially connected shell layers, wherein N is more than or equal to 2; the outlet of the tube layer of the nth-stage tube array reactor is provided with a temperature control element Tn; the nth-stage tube array reactor is provided with a shell feeding main pipe P n and a shell feeding branch pipe B n; the P n is communicated with the shell feeding branch pipe B n, and the shell feeding branch pipe B n comprises at least three branches connected in parallel: branch n1, branch n2, branch n3; the branch n1 and the branch n2 are respectively communicated with the shell layer of the nth-stage tubular reactor; the branch n3 is provided with a flow control element F n, and the branch n3 is communicated with the shell layer of the nth-stage tubular reactor or the shell layer of the n+1th-stage tubular reactor; the temperature control element Tn and the flow control element F n are controlled in cascade; n=any integer from 1 to N.
The cascade control of the invention is that the temperature sensor of the temperature control element Tn and the flow sensor of the flow control element F n are controlled in cascade.
When the branch n3 is communicated with the shell layer of the nth-stage tubular reactor, the interface position is preferably not higher than 100mm above the lower tube plate so as to avoid excessive heating of materials in the tube and difficult control of temperature.
The N (N is more than or equal to 2) level tubular reactors are formed by sequentially connecting tubular layers in series, and the method means that: the pipe layers of the 1 st-level tubular reactor, the pipe layer … … of the 2 nd-level tubular reactor, the pipe layer of the N-level tubular reactor, the pipe layer of the n+1 th-level tubular reactor and the pipe layer of the n+2-level tubular reactor are sequentially communicated through pipelines, and the pipe layer of the … … N-1 th-level tubular reactor and the pipe layer of the N-level tubular reactor are sequentially communicated. Preferably, the outlet of the tube layer of the 1 st stage tube type reactor is communicated with the inlet of the tube layer of the 2 nd stage tube type reactor through a pipeline … …, the outlet of the tube layer of the N stage tube type reactor is communicated with the inlet of the tube layer of the n+1 th stage tube type reactor through a pipeline, the outlet of the tube layer of the n+1 th stage tube type reactor is communicated with the inlet of the tube layer of the n+2 th stage tube type reactor through a pipeline … …, and the outlet of the tube layer of the N-1 th stage tube type reactor is communicated with the inlet of the tube layer of the N stage tube type reactor through a pipeline.
The N (N is more than or equal to 3) level tubular reactors are sequentially connected in series by a shell layer, and refer to: the shell layers of the 1 st-level tubular reactor, the shell layers … … of the 2 nd-level tubular reactor, the shell layers of the N-level tubular reactor, the shell layers of the n+1-level tubular reactor, the shell layers of the n+2-level tubular reactor, the shell layers of the … … -1-level tubular reactor and the shell layers of the N-level tubular reactor are sequentially communicated through pipelines. Preferably, the outlet of the shell layer of the 1 st-stage tubular reactor is communicated with the inlet of the shell layer of the 2 nd-stage tubular reactor through a pipeline, and the outlet of the shell layer of the n-stage tubular reactor and the inlet of the shell layer of the n+1-stage tubular reactor are communicated through a pipeline; the outlet of the shell layer of the n+1-stage tubular reactor and the inlet of the shell layer of the n+2-stage tubular reactor are communicated through a pipeline … …, and the outlet of the shell layer of the N-1-stage tubular reactor is communicated with the inlet of the shell layer of the N-stage tubular reactor through a pipeline.
Optionally, the branches n1 and n2 are communicated with the shell layer of the nth-stage tubular reactor, and are sequentially arranged in the direction from the top end to the bottom end of the tubular reactor.
Optionally, the n1 is communicated with the shell layer of the nth-stage tubular reactor and is close to the top end of the tubular reactor;
optionally, the n2 is communicated with the shell layer of the nth-stage tubular reactor and is close to 1/4-1/6 of the top end of the tubular reactor.
Optionally, in the column tube of the nth stage column tube type reactor, the catalyst and the porcelain balls are sequentially filled in the direction from the bottom end to the top end of the column tube.
Optionally, the ratio of the filling height of the catalyst to the filling height of the porcelain balls is 1:1-5:1, preferably 3:1-4:1.
The catalyst adopted by the tubular organic hydride dehydrogenation reaction system and method is a catalyst commonly used for dehydrogenation reaction of organic liquid hydrogen storage materials, for example: the Pt/Al 2O3 composite catalyst is preferably added with an auxiliary agent Fe and lanthanide, and is preferably a catalyst prepared by Chinese patent application publication No. CN 111054383A.
Alternatively, the ratio of the loading of the n+1 stage shell-and-tube reactor catalyst to the loading of the n stage shell-and-tube reactor catalyst is from 0.5 to 1.5, preferably from 0.9 to 1.1.
Alternatively, the catalyst has a particle size of 1.8-2 mm and is packed into a cylinder having a height of 3-8 mm.
Optionally, the porcelain ball has the specification ofOne of them.
Alternatively, the catalyst and the porcelain balls are separated by a 12-mesh screen.
Optionally, the nth stage tubular reactor is further provided with a heater H n, and the heater H n is disposed between the shell feeding manifold P n and the shell feeding branch B n.
Optionally, the organic hydride dehydrogenation reaction system is further provided with a first heat exchanger E 1; the first heat exchanger E 1 consists of a heat exchange pipeline I and a heat exchange pipeline I' which can perform heat exchange; the organic hydride source, the heat exchange pipeline I and the pipeline layer inlet of the first-stage tubular reactor are sequentially communicated through pipelines; the shell of the nth-stage tubular reactor is provided with a shell discharging pipe Q n; when n=any integer from 1 to N-1, the branch N3 and Qn are combined to be used as a shell feeding main pipe P n+1 of the n+1st-stage tubular reactor; when n=n, the branch N3 is combined with Q n, and then communicated with the heat exchange pipeline I'.
Preferably, the organic hydride dehydrogenation reaction system is further provided with a second heat exchanger E 2, and the second heat exchanger E 2 consists of a heat exchange pipeline II and a heat exchange pipeline II' which can perform heat exchange; the organic hydride source, the heat exchange pipeline II, the heat exchange pipeline I and the pipeline layer inlet of the first-stage tubular reactor are sequentially communicated through pipelines; and the outlet of the tube layer of the Nth-stage tube array reactor is communicated with the heat exchange pipeline II'.
Preferably, when n=n, the branch N3 and the shell discharging pipe Qn are combined and then communicated with two branches in parallel, namely, a branch (n+1) 1 and a branch (n+1) 2; a branch (N+1) 1 is communicated with the heat exchange pipeline I'; the branch (n+1) 2 is provided with a flow control element F N+1; a temperature control element T N+1 is arranged at the inlet of the pipe layer of the first-stage pipe array reactor; the F N+1 is controlled in tandem with the T N+1.
As one embodiment, when n=2, the organic hydride dehydrogenation reaction system includes a two-stage tube type reactor, a first heat exchanger E 1, a second heat exchanger E 2, a heater H 1, and a heater H 2, in which tube layers are sequentially connected in series and shell layers are sequentially connected in series; the first heat exchanger E1 consists of a heat exchange pipeline I and a heat exchange pipeline I' which can exchange heat; the second heat exchanger E2 consists of a heat exchange pipeline II and a heat exchange pipeline II' which can exchange heat; the organic hydride source, the heat exchange pipeline II, the heat exchange pipeline I and the pipeline layer inlet of the first-stage tubular reactor are sequentially communicated; the outlet of the tube layer of the second-stage tube array reactor is communicated with the heat exchange pipeline II'; the outlet of the tube layer of the first-stage tube type reactor and the outlet of the tube layer of the second-stage tube type reactor are respectively provided with a temperature control element T 1、T2; the shell of the first-stage shell-and-tube reactor is provided with a shell feeding main pipe P 1, a shell feeding branch pipe B 1 and a shell discharging pipe Q 1; the shell layer of the second-stage shell-and-tube reactor is provided with a shell layer feeding main pipe P 2, a shell layer feeding branch pipe B 2 and a shell layer discharging pipe Q 2;P1 which are communicated with a shell layer feeding branch pipe B 1 through a heater H 1, wherein the shell layer feeding branch pipe consists of a branch 11, a branch 12 and a branch 13 which are connected in parallel; the branch 11 and the branch 12 are respectively communicated with the shell layer of the first-stage tubular reactor; the shell feeding main pipe P 2;P2 serving as a shell of the second-stage tubular reactor after the branches 13 and Q 1 are combined is communicated with the shell feeding branch pipe B 2 through the heater H 2, and the shell feeding branch pipe B 2 consists of a branch 21, a branch 22 and a branch 23 which are connected in parallel; the branch 21 and the branch 22 are respectively communicated with the shell layer of the second-stage tubular reactor; the branches 23 and Q 2 are converged and then communicated with a heat exchange pipeline I' of the first heat exchanger E 1. The branch 13 and the branch 23 are respectively provided with a flow control element F 1、F2.F1 and a flow control element T 1 for cascade control; f 2 and T 2 are controlled in cascade; preferably, branch 23 merges with Q 2 and communicates with parallel branches 31, 32. The branch 32 is communicated with the heat exchange pipeline I' of the first heat exchanger E 1, and is combined with the heat inlet pipe 31 after heat exchange is carried out on the branch 32 and the heat exchange pipeline I in E 1. The heat pipe 31 is provided with a flow control element F3. The inlet of the tube layer of the first-stage tube-array reactor is provided with temperature control elements T 3;F3 and T 3 for cascade control.
As one embodiment, when n=3, the organic hydride dehydrogenation reaction system includes a three-stage tube type reactor, a first heat exchanger E 1, a second heat exchanger E 2, a heater H 1, a heater H 2, a heater H 3, in which tube layers are sequentially connected in series and shell layers are sequentially connected in series; the first heat exchanger E 1 consists of a heat exchange pipeline I and a heat exchange pipeline I' which can exchange heat; the second heat exchanger E 2 consists of a heat exchange pipeline II and a heat exchange pipeline II' which can exchange heat; the organic hydride source, the heat exchange pipeline II, the heat exchange pipeline I and the pipeline layer inlet of the first-stage tubular reactor are sequentially communicated; the outlet of the tube layer of the third-stage tube array reactor is communicated with the heat exchange pipeline II'; the outlet of the tube layer of the first-stage tube type reactor, the outlet of the tube layer of the second-stage tube type reactor and the outlet of the tube layer of the third-stage tube type reactor are respectively provided with temperature control elements T 1、T2 and T3; the shell of the first-stage shell-and-tube reactor is provided with a shell feeding main pipe P 1, a shell feeding branch pipe B 1 and a shell discharging pipe Q 1; the shell of the second-stage shell-and-tube reactor is provided with a shell feeding main pipe P 2, a shell feeding branch pipe B 2 and a shell discharging pipe Q 2; the shell layer of the third-stage shell-and-tube reactor is provided with a shell layer feeding main pipe P 3, a shell layer feeding branch pipe B 3 and a shell layer discharging pipe Q 3;P1 which are communicated with a shell layer feeding branch pipe B 1 through a heater H 1, wherein the shell layer feeding branch pipe consists of a branch 11, a branch 12 and a branch 13 which are connected in parallel; the branch 11 and the branch 12 are respectively communicated with the shell layer of the first-stage tubular reactor; the shell feeding main pipe P 2.P2 serving as a shell of the second-stage tubular reactor after the branches 13 and Q 1 are combined is communicated with the shell feeding branch pipe B 2 through the heater H 2, and the shell feeding branch pipe B 2 consists of a branch 21, a branch 22 and a branch 23 which are connected in parallel; the branch 21 and the branch 22 are respectively communicated with the shell layer of the second-stage tubular reactor; the branch 23 and Q 2 are converged and then are used as a shell feeding main pipe P 3.P3 of the third-stage tube array reactor to be communicated with a shell feeding branch pipe B 3 through a heater H 3, and the shell feeding branch pipe B 2 comprises a branch 31, a branch 32 and a branch 33 which are connected in parallel; the branch circuits 31 and 32 are respectively communicated with the shell layers of the third-stage tubular reactor, and the branch circuits 33 and Q 3 are combined and then communicated with a heat exchange pipeline I' of the first heat exchanger E 1. The branch 13, the branch 23 and the branch 33 are respectively provided with flow control elements F 1、F2、F3.F1 and T 1 for cascade control; f 2 and T 2 are controlled in cascade; f 3 and T 3 are controlled serially. Preferably, branch 33 is combined with Q 3 and then connected to parallel branches 41 and 42. The branch 42 is communicated with the heat exchange pipeline I' of the first heat exchanger E 1, and is combined with the heat inlet pipe 41 after heat exchange with the heat exchange pipeline I in E 1. The heat intake pipe 41 is provided with a flow control element F4. The inlet of the tube layer of the first-stage tube-array reactor is provided with temperature control elements T 4;F4 and T 4 for cascade control.
In another aspect, the present invention provides a method for dehydrogenating an organic hydride using any one of the above-described organic hydride dehydrogenation reaction systems, comprising: the organic hydride enters the tube layer of the nth-stage tube type reactor, contacts with the catalyst in the tube layer to perform dehydrogenation reaction, and the nth-stage reaction product flows out from the tube layer outlet of the nth-stage tube type reactor and enters the tube layer of the (n+1) th-stage tube type reactor; the heat carrier enters the shell layer of the nth-stage tubular reactor through the branches n1 and n2 to provide heat for dehydrogenation reaction in the tube layer; the flow rate of the branch n3 is regulated by the flow control element F n of the branch n3 to regulate the temperature of the nth stage reaction product at the outlet of the tube layer of the nth stage tube reactor.
Alternatively, the temperature of the first stage reaction product at the outlet of the tube layer of the first stage reactor is from 250 ℃ to 420 ℃, preferably 320 ℃.
Alternatively, the temperature of the second stage reaction product at the outlet of the tube layer of the second stage reactor is from 250 to 420 ℃, preferably 340 ℃.
Alternatively, the temperature of the third stage reaction product at the outlet of the tube layer of the third stage reactor is 250 to 420 ℃, preferably 360 ℃.
Optionally, the organic hydride is vaporized and/or superheated before entering the tube layer of the first-stage tube type reactor; when n=n; the flow rate of the branch (N+1) 2 is regulated by a flow control element F N+1 of the branch (N+1) 2 so as to regulate and control the temperature of the organic hydride at the inlet of the tube layer of the first-stage tube type reactor.
Alternatively, the temperature of the organic hydride at the inlet of the tube layer of the first stage tube array reactor is 280 to 360 ℃, preferably 280 to 300 ℃.
Optionally, the temperature of the organic hydride at the inlet of the tube layer of the nth stage tube reactor is 250-420 ℃.
Optionally, the organic hydride is selected from at least one of a substituted or unsubstituted alkane, a substituted or unsubstituted cycloalkane, a substituted or unsubstituted alkene, a substituted or unsubstituted monocyclic aromatic hydrocarbon, and a substituted or unsubstituted polycyclic aromatic hydrocarbon.
Optionally, the substituted or unsubstituted alkane is selected from at least one of C1-C6 alkanes; preferably propane or butane.
Optionally, the substituted or unsubstituted cycloalkane is selected from at least one of C3-C6 cycloalkanes; preferably cyclohexane or methylcyclohexane.
Optionally, the substituted or unsubstituted alkene is selected from at least one of C2-C6 alkene hydrocarbons; butene is preferred.
Optionally, the substituted or unsubstituted monocyclic aromatic hydrocarbon is selected from at least one of ethylbenzene, dibenzyltoluene, cyclohexylbenzene, dicyclohexylbenzene.
Optionally, the substituted or unsubstituted polycyclic aromatic hydrocarbon is selected from at least one of tetrahydronaphthalene and decalin.
Optionally, the heat carrier is selected from water vapor or molten salt.
Optionally, the molten salt is at least one selected from potassium nitrate, sodium nitrite and sodium nitrate.
Optionally, the molten salt is preferably composed of (40-60) by weight: (30-50): and (5-10) potassium nitrate, sodium nitrite and sodium nitrate.
Alternatively, the molten salt is preferably composed of 53% potassium nitrate, 40% sodium nitrite and 7% sodium nitrate.
Optionally, the flow direction of the organic hydride in the tube layer of the nth-stage tube type reactor and the flow direction of the heat carrier in the shell layer are in a parallel flow mode.
Optionally, in the n-th stage tubular reactor tube layer, the dehydrogenation reaction conditions include: the reaction temperature is 250-420 ℃, preferably 280-400 ℃; the reaction pressure is 0.02 MPaA-1.0 MPaA, preferably 0.1-MPaA-0.4 MPaA; the total mass space velocity of the reaction is 0.5h -1～5h-1, preferably 2h -1～4h-1.
Optionally, in the shell-and-tube feeding header P n of the nth-stage tubular reactor, the flow rate of the heat carrier is 5000-10000 kg/h.
Alternatively, the flow rate of the branch n1 of the shell of the nth stage tubular reactor is 2000 to 3000kg/h, preferably 1600 to 2400kg/h.
Alternatively, the flow rate of the branch n2 of the shell of the nth stage tubular reactor is 1500 to 4000kg/h, preferably 3000 to 3600kg/h, more preferably 2000kg/h.
Alternatively, the flow rate of the branch n3 of the shell of the first-stage tubular reactor is 1000 to 3000kg/h, preferably 1200 to 1600kg/h.
Alternatively, the total mass space velocity of the organic hydride at the inlet of the tube layer of the nth stage tube type reactor is 4-20 h -1.
Alternatively, the temperature of the heat carrier at the inlet of the shell-and-tube reactor of the nth stage is 40 ℃ to 150 ℃, preferably 50 ℃ to 120 ℃, higher than the temperature of the reactants at the inlet of the tube layer.
Alternatively, the temperature of the reactants at the inlet of the n+1 stage shell-and-tube reactor tube layer is 10 ℃ to 60 ℃, preferably 15 ℃ to 35 ℃, preferably 20 ℃ higher than the temperature of the reactants at the inlet of the n stage shell-and-tube reactor tube layer.
Optionally, the flow of the branch n1 of the nth stage tubular reactor accounts for 10% -50%, preferably 20% -30% of the total flow of the shell-and-tube feeding header P n.
The invention divides the heat carrier into three strands after being heated by the nth stage heater, wherein two strands enter the shell layer of the nth stage tubular reactor to provide heat for dehydrogenation reaction in the tube layer, and the third strand enters the n+1th stage heater.
When the catalyst is unevenly filled or even coked and deactivated, the pressure drop in the reactor tube and the flow distribution of hydride in the tube are uneven, so that the mass airspeed and the reaction pressure of the hydride in different tubes are different, the dehydrogenation reaction degree is different, and the uncertain factors can bring unstable operation to the device.
Drawings
FIG. 1 is a schematic diagram of a tubular organic hydride dehydrogenation reaction system (exemplified by a three-stage tubular reactor) according to the present invention;
FIG. 2 is an enlarged schematic view of the first-stage tubular reactor R1 of FIG. 1;
In the figure, a first-stage tubular reactor R 1, a second-stage tubular reactor R 2, a third-stage tubular reactor R 3, a first-stage heater H 1, a second-stage heater H 2, a third-stage heater H 3, a first heat exchanger E 1 and a second heat exchanger E 2 are arranged in the first-stage tubular reactor R 1, the second-stage tubular reactor R 2, the third-stage tubular reactor R 3, the first-stage heater H 1, the second-stage heater H 2 and the third-stage heater H 3;
101 an organic hydride source, 102 an organic hydride vaporized by a first stage heat exchanger, 103 an organic hydride superheated by a second stage heat exchanger, 104a first stage reaction product, 105 a second stage reaction product, 106 a third stage reaction product, 107 a cooled third stage reaction product;
108 heat carrier source, 10 shell feed header P 1, 20 shell feed header P 2, 30 shell feed header P 3, 11 feed tube 1-1, 12 feed tube 1-2, 13 feed tube 1-3, 21 feed tube 2-1, 22 feed tube 2-2, 23 feed tube 2-3, 31 feed tube 3-1, 32 feed tube 3-2, 33 feed tube 3-3, 41 feed tube 4-1, 42 feed tube 4-2, 109.
FC is a flow control element, TC is a temperature control element.
Detailed Description
As a preferred embodiment, the method for dehydrogenating organic hydride by using the tubular reactor organic hydride dehydrogenation system of the invention comprises the following steps:
a, filling porcelain balls and catalysts in the tube layer of the tube type reactor from top to bottom;
b, firstly vaporizing the organic hydride by a second heat exchanger (vaporizer), then heating to an initial reaction temperature by a first heat exchanger (superheater), and then entering a tube layer of a first-stage tubular reactor filled with a catalyst and porcelain balls for dehydrogenation reaction until the organic hydride flows out of the tube layer of an Nth-stage tubular reactor to obtain a reaction product containing hydrogen, wherein N is more than or equal to 2;
c, heating the heat carrier by a first-stage heater, dividing the heat carrier into three strands, wherein the first strand enters a shell layer of the first-stage tubular reactor at the top position of a porcelain ball to provide heat for dehydrogenation reaction in a tube layer, the second strand enters the shell layer of the first-stage tubular reactor at the top position of a catalyst to provide heat for dehydrogenation reaction in the tube layer, and the third strand enters a second-stage heater to heat after being mixed with the heat carrier at the shell layer outlet of the first-stage tubular reactor, and then enters the shell layer of the second-stage tubular reactor until the heat carrier flows out from the shell layer of the Nth-stage tubular reactor;
d, taking a reaction product containing hydrogen flowing out of a tube layer of the Nth-stage tube type reactor as a heat source of a second heat exchanger (vaporizer) in the step a, dividing the shell-and-tube outlet heat carrier of the Nth-stage tube type reactor into two parts, taking the first part as the heat source of the first heat exchanger (superheater) in the step a, mixing the first part with the second part, and then merging the mixed part into a steam pipe network;
Step b, controlling the temperature of an organic hydride outlet of a second heat exchanger (a superheater), controlling the flow rate of a first heat carrier in step d, and controlling the temperature of the organic hydride outlet to be 280-360 ℃ through the flow rate of the first heat carrier;
f, a first strand of heat carrier in the step c is provided with constant flow control, a second strand of heat carrier is not provided with flow control, a third strand of heat carrier is provided with flow control, the outlet product of the first-stage tubular reactor in the step a is provided with temperature control, the temperature control cascade is connected with the flow control cascade of the third strand of heat carrier in the step c, and the outlet temperature of the first-stage reactor is controlled to be 250-420 ℃ by controlling the flow of the third strand;
g repeating the step f, so that the inlet temperature of the second-stage to N-th-stage reactors is effectively controlled between 250 ℃ and 420 ℃.
Example 1 tubular organic hydride dehydrogenation reaction System
As shown in fig. 1 and 2, the tubular organic hydride dehydrogenation reaction system mainly comprises a first-stage tubular reactor R 1, a second-stage tubular reactor R 2, a third-stage tubular reactor R 3, a first-stage heater H 1, a second-stage heater H 2, a third-stage heater H 3, a first heat exchanger E 1 and a second heat exchanger E 2. The heat exchanger E 1 consists of a heat exchange pipeline I and a heat exchange pipeline I' which can exchange heat; the second heat exchanger E 2 is composed of a heat exchange pipeline II and a heat exchange pipeline II' which can exchange heat.
R 1、R2、R3 has the same tube specification, isThe length of the tube is 4 meters, the number of the tubes is 1600, and the diameter of the shell layer (the reactor cylinder) is 1500mm.
Wherein, the inside of the tube array of R 1 is sequentially filled with a catalyst and porcelain balls from bottom to top; the filling height ratio of the catalyst to the porcelain ball is 3:1; the filling height of the catalyst is 3 meters, and the filling height of the porcelain ball is 1 meter; the catalyst and the porcelain balls are sequentially filled in the R 2 from bottom to top, the filling height ratio of the catalyst to the porcelain balls is 4:1, the filling height of the catalyst is 3.2 meters, and the filling height of the porcelain balls is 0.8 meter; the inside of R 3 is filled with catalyst and ceramic balls in sequence from bottom to top, the filling height ratio of the catalyst to the ceramic balls is 5:1, the filling height of the catalyst is 3.34 meters, and the filling height of the ceramic balls is 0.66 meter.
The tube layer outlet of R 1 (at the bottom of R 1) communicates with the inlet of the tube layer of R 2 (at the top of R 2); the tube layer outlet of R 2 (at the bottom of R 2) communicates with the inlet of the tube layer of R 3 (at the top of R 3); the outlet of the tube layer of R 3 (positioned at the bottom of R 3) is communicated with the heat exchange pipeline II' of the second heat exchanger E 2, and exchanges heat with the heat exchange pipeline II of E 2.
The heat carrier source 108 is communicated with a shell feeding header P 1,P1 of the first-stage tubular reactor and is communicated with an inlet of the first heater H 1, and an outlet of the H 1 is communicated with a shell feeding branch pipe, wherein the shell feeding branch pipe consists of a heat inlet pipe 1-1, a heat inlet pipe 1-2 and a heat inlet pipe 1-3 which are connected in parallel; the heat inlet pipe 1-1 is communicated with a shell layer of R 1 at a position corresponding to the top of the porcelain ball in R 1; the heat inlet pipe 1-2 is communicated with the shell layer of R 1 at the corresponding position of the top of the catalyst in R 1. The heat pipe 1-1 is provided with a flow control element FC01, and the heat pipe 1-3 is provided with a flow control element FC02.
The shell outlet (positioned at the lower part of R 1) of R 1 is communicated with a shell discharging pipe Q 1, a shell feeding main pipe P 2,P2 which is used as a shell feeding main pipe of a second-stage tubular reactor after the heat inlet pipe 1-3 and the Q 1 are combined is communicated with the inlet of a second heater H 2, and the outlet of H 2 is communicated with a heat inlet pipe 2-1, a heat inlet pipe 2-2 and a heat inlet pipe 2-3 which are connected in parallel; the heat inlet pipe 2-1 is communicated with a shell layer of R 2 at a position corresponding to the top of the porcelain ball in R 2; the heat inlet pipe 2-2 is communicated with the shell layer of R 2 at the corresponding position of the top of the catalyst in R 2. The heat inlet pipe 2-1 is provided with a flow control element FC03, and the heat inlet pipe 2-3 is provided with a flow control element FC04.
The shell outlet (positioned at the lower part of R 2) of R 2 is communicated with a shell discharging pipe Q 2, the heat inlet pipe 2-3 is combined with Q 2 and then is used as the inlet of H 3 communicated with the shell feeding main pipe P 3,P3 of the third-stage tube array reactor, and the outlet of H 3 is communicated with a heat inlet pipe 3-1, a heat inlet pipe 3-2 and a heat inlet pipe 3-3 which are connected in parallel; the heat inlet pipe 3-1 is communicated with a shell layer of R 3 at a position corresponding to the top of the porcelain ball in R 3; the heat inlet pipe 3-2 is communicated with the shell layer of R 3 at the corresponding position of the top of the catalyst in R 3. The heat inlet pipe 3-1 is provided with a flow control element FC05; the heat intake pipe 33 is provided with a flow control element FC06.
The shell outlet (positioned at the lower part of R 3) of R 3 is communicated with a shell discharging pipe Q 3, and the heat inlet pipe 3-3 and the heat inlet pipe Q 3 are combined and then communicated with a parallel heat inlet pipe 4-1 and a parallel heat inlet pipe 4-2. The heat inlet pipe 4-2 is communicated with a heat exchange pipeline I' of the first heat exchanger E 1, exchanges heat with the heat exchange pipeline I in E 1, and is combined with the heat inlet pipe 4-1. The heat pipe 4-1 is provided with a flow control element FC07.
The organic hydride source 101 is sequentially communicated with a heat exchange pipeline II of the second heat exchanger E 2 and a heat exchange pipeline I of the first heat exchanger E 1; the heat exchange pipeline I is communicated with a pipeline layer inlet (positioned at the top of R 1) of the R 1, and a temperature control element TC07 is arranged on the communicated pipeline or the pipeline layer inlet of the R 1.
A temperature control element TC02 is arranged at the outlet of the tube layer of the tube array of R 1; the outlet of the tube layer of the tube array of R 2 is provided with a temperature control element TC04; the outlet of the tube layer of the tube array of R 3 is provided with a temperature control element TC06.
The flow control element FC02 is in cascade with the temperature control element TC02, the flow control element FC04 is in cascade with the temperature control element TC04, the flow control element FC06 is in cascade with the temperature control element TC06, and the flow control element FC07 is in cascade with the temperature control element TC 07.
Example 2 organic hydride dehydrogenation process
A thousand tons of hydrogen devices take methylcyclohexane as a dehydrogenation raw material, a dehydrogenation reaction process technology of a tubular organic hydride dehydrogenation reaction system (shown in fig. 1 and 2) in the embodiment 1 is adopted, a heat carrier is saturated water vapor of 1.0MPaA, and main working conditions and operation conditions are shown in table 1.
The conversion of methylcyclohexane is calculated according to formula (1)
When the methylcyclohexane conversion rate in the nth stage reactor is calculated, according to formula (1), in formula (1), m 1 is the mass of methylcyclohexane at the inlet of the nth stage reactor, m 2 is the mass of methylcyclohexane at the outlet of the nth stage reactor, and n=1 to N.
When calculating the total conversion of methylcyclohexane in a tubular organic hydride dehydrogenation reaction system, the total conversion is calculated according to formula (1), wherein m 1 is the mass of methylcyclohexane at the inlet of the 1 st stage reactor, m 2 is the mass of methylcyclohexane at the outlet of the N-th stage reactor, and N is 3 in example 2.
In the embodiment of the invention, the catalyst prepared in the embodiment 1 in the Chinese patent application publication CN111054383A is adopted; the ceramic ball is made of inert alumina with particle sizePurchased from the petrochemical filler plant in Duckweed country city, jiangxi province.
Flow direction of heat carrier (water vapor) in shell-and-tube reactor:
After being heated by the first-stage heater H 1, the heat carrier 108 (water vapor) is divided into three parts, namely a heat carrier 1-1, a heat carrier 1-2 and a heat carrier 1-3, by a heat inlet pipe 1-1, a heat inlet pipe 1-2 and a heat inlet pipe 1-3. The flow of heat carrier 1-1 is 30% of the total heat carrier (heat carrier 108) flow. Wherein, the heat carrier 1-1 and the heat carrier 1-2 enter the shell layer of R 1 to provide heat for the dehydrogenation reaction in the R 1 tube layer, the heat carrier 1-1 enters the shell layer of R 1 at the position corresponding to the top of the porcelain ball, and the heat carrier 1-2 enters the shell layer of R 1 at the position corresponding to the top of the catalyst; both the heat carrier 1-1 and the heat carrier 1-2 flow out from the shell outlet of R 1 (positioned at the lower part of R 1), are mixed with the heat carrier 1-3, and enter the second-stage heater H 2 for heating. After heating, the heat flows into the heat inlet pipe 2-1, the heat inlet pipe 2-2 and the heat inlet pipe 2-3 to form three strands, namely a heat carrier 2-1, a heat carrier 2-2 and a heat carrier 2-3, wherein the heat carrier 2-1 accounts for 25% of the total flow.
The heat carrier 2-1 and the heat carrier 2-2 enter the shell layers of R 2, flow out from the shell layer outlet (positioned at the lower part of R 2) of R 2, then are mixed with the heat carrier 2-3, enter a third-stage heater H 3 for heating, and are divided into three strands by a heat inlet pipe 3-1, a heat inlet pipe 3-2 and a heat inlet pipe 3-3 after heating, namely the heat carrier 3-1, the heat carrier 3-2 and the heat carrier 3-3, wherein the heat carrier 3-1 accounts for 20% of the total flow.
The heat carrier 3-1 and the heat carrier 3-2 enter the shell layer of R 3, flow out from the shell layer outlet of R 3 (positioned at the lower part of R 3), are mixed with the heat carrier 3-3, are divided into two streams by the heat inlet pipe 4-1 and the heat inlet pipe 4-2, respectively are the heat carrier 4-1 and the heat carrier 4-2, and the heat carrier 4-2 flows through the heat exchange pipeline I' of the first heat exchanger E 1 to serve as a heat source of the heat exchange pipeline I of E 1, flows out from E 1, is mixed with the heat carrier 4-1, and is then integrated into a steam pipe network.
Flow direction of organic hydride (methylcyclohexane) in R 1、R2、R3 tube layer:
Methylcyclohexane 101 first flows through heat exchange line II of second heat exchanger E 2, is heated to vaporize (vaporization temperature is 145 ℃) by R 3 tube layer outlet product 106 in heat exchange line II ', then flows through heat exchange line I of first heat exchanger E 1, is heated therein to an initial reaction temperature (i.e. TC07 at 300 ℃) by heat carrier 4-2 in heat exchange line I', then enters R 1 tube layer from R 1 tube layer inlet (at the top of R 1) to undergo a first stage dehydrogenation reaction, and outlet product 104 of R 1 is discharged from the tube layer outlet (at the bottom of R 1) of R 1. Then, the dehydrogenation reaction of the second stage and the dehydrogenation reaction of the third stage respectively occur after the dehydrogenation reaction sequentially enter the interior of R 2、R3(R2 and the interior of R 3 and the flow direction of the interior of R 1 is consistent, wherein the initial reaction temperature entering R 2 is 320 ℃, the initial reaction temperature entering R 3 is 340 ℃, and the final product flows out from the pipe layer outlet (positioned at the bottom of R 3) of R 3 to obtain the outlet product 106R 3 of the outlet product 106R 3 containing hydrogen, and the outlet product 106 flows through the heat exchange pipeline II' of the second heat exchanger E 2 to serve as a heat source of the heat exchange pipeline II of the second heat exchanger E 2.
Since FC02 and TC02 cascade, there is some variation in the heat inside the reactor during the reaction, and in order to maintain TC02 at a constant value, the flow rate of FC02 fluctuates with fluctuation in the reaction performance in the reactor, so the second and third strands are fluctuating values.
Temperature regulation:
The inlet of the pipe layer of R 1 is provided with a temperature control TC07, the temperature TC07 of the inlet of the pipe layer of R 1 is regulated by controlling the flow of the FC07, and the temperature of TC07 is controlled at 300 ℃;
The outlet of the tube layer of R 1 is provided with temperature control TC02, the heat carrier 1-1 is controlled by constant flow, namely FC01, accounting for 30% of the total heat carrier flow P 1, no flow control is arranged on the pipeline of the heat carrier 1-2, the heat carrier 1-3 is a free pipeline, the FC02 and the TC02 are in cascade, the flow of the heat carrier 1-3 is controlled by the FC02 to regulate the temperature TC02 of the outlet of the tube layer of R 1, and the temperature of the TC02 is controlled at 320 ℃;
The inlet temperature control of the pipe layer of R 2 is the outlet temperature TC02 of the pipe layer of R1;
The outlet of the tube layer of R 2 is provided with temperature control TC04, the heat carrier 2-1 is controlled by constant flow, namely FC03, accounting for 25% of the total heat carrier flow P 2 (the flow of P2 is the same as that of P1), the heat carrier 2-2 is not controlled by flow, and is a free pipeline, the heat carrier 2-3 is provided with flow control FC04, FC04 and TC04 are in cascade, the temperature TC04 of the outlet of the tube layer of R 2 is regulated by controlling the flow FC04 of the heat carrier 2-3, and the temperature of TC04 is controlled at 340 ℃;
The inlet temperature control of the pipe layer of R 3 is the outlet temperature TC04 of the pipe layer of R1;
The outlet of the tube layer of R 3 is provided with temperature control TC06, the heat carrier 3-1 is controlled by constant flow, namely FC05, accounting for 20% of the total heat carrier flow, no flow control is arranged on the pipeline of the heat carrier 3-2, the heat carrier 3-3 is a free pipeline, the FC06 and the TC06 are in cascade, the temperature TC06 of the outlet of the tube layer of R 3 is regulated by controlling the flow FC06 of the heat carrier 3-3, and the temperature of the TC06 is controlled at 360 ℃;
The organic hydride outlet in superheater E 4 is the tube layer inlet temperature of R 1, TC07.
TABLE 1
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Claims (10)
1. The organic hydride dehydrogenation reaction system is characterized by comprising N-level tubular reactors with sequentially connected tube layers and sequentially connected shell layers, wherein N is more than or equal to 2;
The outlet of the tube layer of the nth-stage tube array reactor is provided with a temperature control element Tn;
The nth-stage tube array reactor is provided with a shell feeding main pipe P n and a shell feeding branch pipe B n;
The P n is communicated with the shell feeding branch pipe B n, and the shell feeding branch pipe B n comprises at least three branches connected in parallel: branch n1, branch n2, branch n3;
The branch n1 and the branch n2 are respectively communicated with the shell layer of the nth-stage tubular reactor;
the branch n3 is communicated with the shell layer of the nth-stage tubular reactor or the shell layer of the n+1th-stage tubular reactor;
Branch n3 is provided with a flow control element F n;
The temperature control element Tn and the flow control element F n are controlled in cascade;
n=any integer from 1 to N.
2. The organic hydride dehydrogenation reaction system according to claim 1, wherein,
The branches n1 and n2 are communicated with the shell layer of the nth-stage tubular reactor and are sequentially arranged in the direction from the top end to the bottom end of the tubular reactor;
Preferably, the n1 is communicated with the shell layer of the nth-stage tubular reactor and is close to the top end of the tubular reactor;
Preferably, the n2 is communicated with the shell layer of the nth-stage tubular reactor and is close to 1/4-1/6 of the top end of the tubular reactor.
3. The organic hydride dehydrogenation reaction system according to claim 1, wherein,
In a tube array of the nth-stage tube array reactor, a catalyst and porcelain balls are sequentially filled in the direction from the bottom end to the top end of the tube array;
Preferably, the ratio of the loading of the catalyst in the n+1-stage tubular reactor to the loading of the catalyst in the n-stage tubular reactor is 0.5 to 1.5, preferably, the ratio is 0.9 to 1.1;
and/or the ratio of the filling height of the catalyst to the filling height of the porcelain ball is 1:1-5:1, preferably 3:1-4:1;
and/or the particle size of the catalyst is 1.8-2 mm.
4. An organic hydride dehydrogenation reaction system according to claim 1 to 3, characterized in that,
The nth-stage tubular reactor is also provided with a heater H n, and the heater H n is arranged between the shell feeding main pipe P n and the shell feeding branch pipe B n;
And/or, the organic hydride dehydrogenation reaction system is also provided with a first heat exchanger E 1; the first heat exchanger E 1 consists of a heat exchange pipeline I and a heat exchange pipeline I' which can perform heat exchange; the organic hydride source, the heat exchange pipeline I and the pipe layer inlet of the first-stage tubular reactor are sequentially communicated;
The nth-stage tube array reactor is provided with a shell-layer discharging tube Q n;
when n=any integer from 1 to N-1, the branch N3 is combined with the shell-side discharging pipe Qn to be used as a shell-side feeding main pipe P n+1 of the n+1th-stage tubular reactor;
When n=n, the branch N3 and the shell discharging pipe Q n are combined and then communicated with the heat exchange pipeline I';
Preferably, the organic hydride dehydrogenation reaction system is further provided with a second heat exchanger E 2; the second heat exchanger E 2 consists of a heat exchange pipeline II and a heat exchange pipeline II' which can perform heat exchange; the organic hydride source, the heat exchange pipeline II, the heat exchange pipeline I and the pipeline layer inlet of the first-stage tubular reactor are sequentially communicated; the outlet of the tube layer of the Nth-stage tube array reactor is communicated with the heat exchange pipeline II';
Preferably, when n=n; the branch N3 and the shell discharging pipe Qn are combined and then communicated with two branches in parallel, namely a branch (N+1) 1 and a branch (N+1) 2; a branch (N+1) 1 is communicated with the heat exchange pipeline I'; the branch (n+1) 2 is provided with a flow control element F N+1; a temperature control element T N+1 is arranged at the inlet of the pipe layer of the first-stage pipe array reactor; the F N+1 is controlled in tandem with the T N+1.
5. A method for dehydrogenating an organic hydride using the organic hydride dehydrogenation reaction system as claimed in any one of claims 1 to 4, comprising:
The organic hydride enters the tube layer of the nth-stage tube type reactor, contacts with the catalyst in the tube layer to perform dehydrogenation reaction, and the nth-stage reaction product flows out from the tube layer outlet of the nth-stage tube type reactor and enters the tube layer of the (n+1) th-stage tube type reactor; the heat carrier enters the shell layer of the nth-stage tubular reactor through the branches n1 and n2 to provide heat for dehydrogenation reaction in the tube layer; the flow rate of the branch n3 is regulated by the flow control element F n of the branch n3 to regulate the temperature of the nth stage reaction product at the outlet of the tube layer of the nth stage tube reactor.
6. A process for the dehydrogenation of an organic hydride according to claim 5, characterized in that,
The temperature of the first stage reaction product at the outlet of the first stage reactor tube layer is 250-420 ℃, preferably 320 ℃;
And/or the temperature of the second stage reaction product at the outlet of the second stage reactor tube layer is 250-420 ℃, preferably 340 ℃;
and/or the temperature of the third stage reaction product at the outlet of the third stage reactor tube layer is 250-420 ℃, preferably 360 ℃;
and/or the organic hydride is gasified and/or overheated before entering the tube layer of the first-stage tube type reactor;
And/or the flow direction of the organic hydride in the tube layer of the nth-stage tube type reactor and the flow direction of the heat carrier in the shell layer are in a parallel flow mode;
And/or when n=n; the flow of the branch (N+1) 2 is regulated by a flow control element F N+1 of the branch (N+1) 2 so as to regulate and control the temperature of the organic hydride at the inlet of the tube layer of the first-stage tube type reactor;
Preferably, the temperature of the organic hydride at the inlet of the tube layer of the first-stage tube array reactor is 280-360 ℃, preferably 280-300 ℃; and/or the temperature of the organic hydride at the inlet of the tube layer of the nth-stage tube type reactor is 250-420 ℃.
7. The method according to claim 5 or 6, wherein,
The organic hydride is selected from at least one of substituted or unsubstituted alkane, substituted or unsubstituted cycloalkane, substituted or unsubstituted alkene, substituted or unsubstituted monocyclic aromatic hydrocarbon, and substituted or unsubstituted polycyclic aromatic hydrocarbon;
Preferably, the substituted or unsubstituted alkane is selected from at least one of C1-C6 alkanes; preferably propane or butane; and/or, the substituted or unsubstituted cycloalkane is selected from at least one of C3-C6 cycloalkanes; preferably cyclohexane or methylcyclohexane; and/or, the substituted or unsubstituted alkene is selected from at least one of C2-C6 alkene hydrocarbons; preferably butene; and/or the substituted or unsubstituted monocyclic aromatic hydrocarbon is selected from at least one of ethylbenzene, dibenzyltoluene, cyclohexylbenzene and dicyclohexylbenzene; and/or the substituted or unsubstituted polycyclic aromatic hydrocarbon is selected from at least one of tetrahydronaphthalene and decalin.
8. The method according to any one of claims 5 to 7, wherein,
The heat carrier is selected from steam or molten salt;
preferably, the molten salt is at least one selected from potassium nitrate, sodium nitrite and sodium nitrate;
preferably, the molten salt consists of the following components in percentage by weight (40-60): (30-50): potassium nitrate, sodium nitrite and sodium nitrate in the (5-10);
Preferably, the molten salt consists of 53% potassium nitrate, 40% sodium nitrite and 7% sodium nitrate.
9. The method according to any one of claims 5 to 8, wherein,
In the tube layer of the nth-stage tubular reactor, the dehydrogenation reaction conditions comprise: the reaction temperature is 250-420 ℃, preferably 280-400 ℃; the reaction pressure is 0.02 MPaA-1.0 MPaA, preferably 0.1-MPaA-0.4 MPaA; the total mass space velocity of the reaction is 0.5h -1～5h-1, preferably 2h -1～4h-1;
And/or, in the shell-and-tube feeding header P n of the nth-stage tubular reactor, the flow rate of the heat carrier is 5000-10000 kg/h;
the flow rate of the branch n1 of the shell layer of the nth-stage tubular reactor is 2000-3000 kg/h, preferably 1600-2400 kg/h;
The flow rate of the branch n2 of the shell layer of the nth-stage tubular reactor is 1500-4000 kg/h, preferably 3000-3600 kg/h;
The flow rate of the branch n3 of the shell layer of the nth-stage tubular reactor is 1000-3000 kg/h, preferably 1200-1600 kg/h;
the total mass airspeed of the organic hydride at the inlet of the tube layer of the nth-stage tube type reactor is 4-20 h -1.
10. The method according to any one of claims 7 to 9, wherein,
The temperature of the heat carrier at the inlet of the shell-and-tube reactor of the nth stage is 40-150 ℃, preferably 50-120 ℃ higher than the temperature of the reactant at the inlet of the tube layer;
And/or the temperature of the reactant at the inlet of the n+1th-stage tubular reactor tube layer is 10 ℃ to 60 ℃, preferably 15 ℃ to 35 ℃, preferably 20 ℃ higher than the temperature of the reactant at the inlet of the n-stage tubular reactor tube layer;
And/or, the flow of the branch n1 of the nth-stage tubular reactor accounts for 10% -50%, preferably 20% -30% of the total flow of the shell-and-tube feeding header P n.
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