CN110559842B - Propylene gas catalytic deoxidation device and method with temperature and tail oxygen concentration control - Google Patents
Propylene gas catalytic deoxidation device and method with temperature and tail oxygen concentration control Download PDFInfo
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- CN110559842B CN110559842B CN201810571382.1A CN201810571382A CN110559842B CN 110559842 B CN110559842 B CN 110559842B CN 201810571382 A CN201810571382 A CN 201810571382A CN 110559842 B CN110559842 B CN 110559842B
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- 239000007789 gas Substances 0.000 title claims abstract description 157
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000001301 oxygen Substances 0.000 title claims abstract description 71
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 71
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000010992 reflux Methods 0.000 claims abstract description 32
- 239000012071 phase Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011805 ball Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 7
- -1 ethylene, propylene Chemical group 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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Abstract
The invention discloses a propylene gas catalytic deoxidation device with temperature and tail oxygen concentration control and a method, and relates to the technical field of chemical tail gas treatment. After heat exchange of raw material propylene tail gas by a heat exchanger, further heating the raw material propylene tail gas to a reaction operation temperature by an electric heater, entering a deoxygenation reactor, wherein a catalyst bed layer is arranged in the deoxygenation reactor, after heat exchange of gas after deoxygenation reaction and raw material gas, cooling the gas by an air condenser, entering a gas-liquid separation tank, separating a liquid phase generated in the reaction process, boosting the gas phase by a compressor, entering a noncondensable gas separation tower, separating the noncondensable gas from the gas phase, and obtaining pure propylene from the liquid phase; and a tail oxygen analyzer is arranged on the fourth outlet pipeline, can detect the content of tail oxygen, and carries out reflux treatment through the fourth outlet branch pipeline if the content of tail oxygen is higher than a normal value. The invention is especially suitable for the process treatments of bed temperature runaway, tail oxygen content overproof and the like which are possibly generated due to oxygen content fluctuation, catalyst activity reduction and the like in the olefin deoxidation process.
Description
Technical Field
The invention relates to the technical field of chemical tail gas treatment, in particular to a propylene gas catalytic deoxidation device and method with temperature and tail oxygen concentration control.
Background
Oxygen-containing organic hydrocarbon gas or tail gas is common gas in the processes of chemical production, storage and transportation at present, for example, organic tail gas in oxidation and peroxidation processes, tail gas of a tank area communication system, landfill gas and the like, and the explosion risk is often caused due to high oxygen content; and SH 3009-. Therefore, in order to reduce the risk of explosion, recycle the organic gas, or ensure that the oxygen-containing organic tail gas meets the emission requirements, the oxygen-containing organic gas or tail gas needs to be deoxidized. For propylene oxide devices, including traditional chlorohydrination propylene oxide devices and hydrogen peroxide method propylene oxide devices applied in recent years, the oxygen content in propylene tail gas fluctuates within the range of 0.5-8%, the oxygen content of the propylene tail gas cannot be discharged into a combustible gas discharge system according to the requirements of the specifications, and the oxygen content needs to be reduced to be below 0.5% for discharge or reduced to be below 0.1% for recycling.
The deoxidation technology in the prior art mainly comprises pressure swing adsorption deoxidation, chemical adsorption deoxidation, activated carbon combustion deoxidation and catalytic combustion deoxidation, wherein the physical and chemical adsorption deoxidation load is small, the deoxidation technology is suitable for removing trace oxygen, the activated carbon deoxidation temperature is high, and the energy consumption is high. The existing catalytic deoxidation technology basically needs to add H2And the like, and the separation of the reducing gas becomes a problem which is difficult to solve. Currently, the catalytic oxidation deoxidation technology for organic gas in the prior art is mainly used for methane-containing gas such as coal bed gas, landfill gas and the like, and the deoxidation technology for olefins such as ethylene, propylene and the like is only suitable for removing ppm-level trace oxygen, and the catalytic deoxidation technology for olefins such as ethylene, propylene and the like is not available.
Disclosure of Invention
The invention aims to provide a propylene gas catalytic deoxidation device and method with temperature and tail oxygen concentration control, which do not need to add H2The reducing gas is equal, and propylene and oxygen are directly reacted to generate CO2And H2O, the purpose of propylene tail gas deoxidation is achieved, the reaction device is safe, environment-friendly and energy-saving, and the device is particularly suitable for solving the problems of temperature runaway of a catalytic bed layer, overproof tail oxygen content and the like possibly caused by oxygen content fluctuation, catalyst activity reduction and the like in the olefin deoxidation process.
The technical solution comprises:
a propylene gas catalytic deoxidation device with temperature and tail oxygen concentration control comprises a heat exchanger, an electric heater, a deoxidation reactor, an air condenser, a gas-liquid separation tank, a compressor and a separation tower, wherein the heat exchanger is provided with a first inlet, a second inlet, a first outlet and a second outlet, the first inlet is opposite to the second outlet, the first inlet is connected with a first inlet pipeline, and the first inlet pipeline is used for feeding raw material propylene tail gas into the heat exchanger; the outlet is connected with a first outlet pipeline;
the other end of the first outlet pipeline is connected with the inlet end of the electric heater, and the outlet end of the electric heater is connected with the inlet end of the deoxygenation reactor;
the outlet end of the deoxygenation reactor is connected with a second outlet pipeline, the other end of the second outlet pipeline is connected to the second inlet, a first temperature monitor is arranged on the second outlet pipeline, and the first temperature monitor is used for monitoring the temperature of gas discharged through the second outlet pipeline;
the second outlet is connected with a third outlet pipeline, the third outlet pipeline is connected with the inlet end of the air condenser, the outlet end of the air condenser is connected with the inlet end of the gas-liquid separation tank, the gas-liquid separation tank is provided with a third outlet and a fourth outlet, the third outlet is used for discharging gas phase, the fourth outlet is used for discharging liquid phase, the third outlet is connected with a fourth outlet pipeline, a fourth outlet branch pipeline is arranged on the fourth outlet pipeline, the other end of the fourth outlet branch pipeline is connected with the first inlet pipeline, and the fourth outlet branch pipeline is used for sending the discharged overproof tail oxygen gas into the heat exchanger for reflux treatment;
a tail oxygen analyzer is arranged on the fourth outlet pipeline, and a second temperature monitor is arranged on the electric heater;
the other end of the fourth outlet pipeline is connected to the inlet end of the compressor, the outlet end of the compressor is connected to the inlet end of the separation tower, the separation tower is provided with an outlet five and an outlet six, the outlet five is used for discharging a gas phase, and the outlet six is used for discharging a liquid phase.
In a preferred embodiment of the present invention, the propylene gas has the following composition in terms of volume percentage concentration: 0.5 to 8 percent of oxygen, 20 to 95 percent of propylene and the balance of nitrogen, carbon dioxide and hydrogen.
As another preferable scheme of the invention, the deoxygenation reactor is a fixed bed adiabatic reactor, the operation pressure is 0-4 MPa, and the reaction operation temperature is 100-430 ℃.
Further, a catalyst bed layer is arranged in the deoxygenation reactor, the outlet temperature of the catalyst bed layer is 200-600 ℃, and the space velocity of the propylene gas in the catalyst bed layer is 500-50000hr-1。
Furthermore, the catalyst selected by the catalyst bed layer comprises a main catalyst and an auxiliary catalyst, the main catalyst is a noble metal catalyst, and the auxiliary catalyst is one or a mixture of more of oxides of soil, alkali metals or alkaline earth metals.
Furthermore, the noble metal catalyst contains one or more active components of Pt, Pd, Ru, Rh, Ag and Ir.
Furthermore, the carrier selected by the catalyst is alumina balls, silica balls, titanium dioxide, molecular sieve, active carbon or carbon nano tubes.
Another task of the present invention is to provide a catalytic deoxygenation method for propylene gas with temperature and tail oxygen concentration control, which adopts the catalytic deoxygenation device, wherein the deoxygenation method comprises:
a, propylene gas enters a heat exchanger through a first inlet pipeline, is discharged from a first outlet after being subjected to heat exchange by the heat exchanger, and enters the electric heater through a first outlet pipeline;
the propylene gas comprises the following components in percentage by volume: 0.5 to 8 percent of oxygen, 20 to 95 percent of propylene, and the balance of nitrogen, carbon dioxide and a small amount of hydrogen;
b, heating the mixture to a temperature required by the reaction by an electric heater, and reacting the mixture in a deoxygenation reactor, wherein the operating pressure in the deoxygenation reactor is 1-3 MPa, and the reaction operating temperature is 100-430 ℃;
c, discharging the gas after the deoxidation reaction through a second outlet pipeline, measuring the temperature of the discharged gas through a first temperature monitor, feeding the gas after the deoxidation reaction into the heat exchanger, exchanging heat with the feed gas, cooling through an air condenser, feeding the gas into the gas-liquid separation tank, and separating a liquid phase generated in the reaction process through an outlet;
d, separating out a gas phase through an outlet, analyzing the tail oxygen content through a tail oxygen analyzer, controlling gas backflow through a valve on a fourth branch pipeline when the tail oxygen content is larger than or equal to 0.15%, cutting off backflow until the tail oxygen content is smaller than 0.15%, boosting the gas phase through a compressor, then feeding the gas phase into a separation tower, separating out noncondensable gas through the gas phase, and obtaining pure propylene through a liquid phase.
Further, the gas phase reflux amount is controlled by the temperature measured by the first temperature monitor.
Further, when the temperature measured by the first temperature monitor is greater than or equal to 550 ℃ and less than 560 ℃, controlling 10% of gas reflux; when the temperature measured by the first temperature monitor is higher than or equal to 560 ℃ and lower than 570 ℃, controlling 15% of gas reflux; when the temperature measured by the first temperature monitor is greater than or equal to 570 ℃ and less than 580 ℃, controlling 20% of gas to flow back; when the temperature measured by the first temperature monitor is greater than or equal to 580 ℃ and less than 590 ℃, controlling 30% of gas reflux; when the temperature measured by the first temperature monitor is greater than or equal to 590 ℃ and less than 600 ℃, controlling 40% of gas reflux; when the temperature measured by the first temperature monitor is more than or equal to 600 ℃, 50 percent of gas reflux is controlled.
In the prior art, the catalytic oxidation deoxidation technology for organic gas mainly aims at methane-containing gas such as coal bed gas, landfill gas and the like, and the deoxidation technology for olefin such as ethylene, propylene and the like is only suitable for removing ppm-level trace oxygen, and the catalytic deoxidation technology for olefin such as ethylene, propylene and the like is not available, but carbon deposition is easily generated on the surface of a catalyst at a certain temperature by olefin.
The invention relates to a propylene gas catalytic deoxidation method with temperature and tail oxygen concentration control, which does not need to add H2The reducing gas is equal, and propylene and oxygen are directly reacted to generate CO2And H2O, can inhibit the generation of carbon deposition on the surface of the catalyst and the generation of a byproduct CO, and achieves the aim of removing the propylene tail gasThe purpose of the oxygen. The invention provides a propylene gas catalytic deoxidation reaction device with automatic control and a method thereof, which are researched aiming at the problems of bed temperature runaway, excessive tail oxygen content and the like possibly caused by oxygen content fluctuation, catalyst activity reduction and the like in the olefin deoxidation process.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of the catalytic deoxygenation process of propylene gas according to the present invention;
in the figure, 1-heat exchanger, 2-electric heater, 3-deoxygenation reactor, 4-air condenser, 5-gas-liquid separation tank, 6-compressor and 7-noncondensable gas separation tower.
Detailed Description
The invention provides a propylene gas catalytic deoxidation device with temperature and tail oxygen concentration control and a method thereof, and in order to make the advantages and technical scheme of the invention clearer and more clear, the invention is described in detail with reference to specific embodiments.
The raw material propylene tail gas of the invention comprises: the volume percentage concentration of the oxygen is 0.5-8%; the volume percentage concentration of the propylene is 20-95 percent, and the rest is nitrogen, carbon dioxide, a small amount of hydrogen and organic gas.
The deoxygenation reactor is a fixed bed adiabatic reactor, the operating pressure is 0-4 MPa, the reaction operating temperature is 100--1。
Percentage concentration of oxygen in reaction tail gas<0.2%, selectivity to CO<0.5％，CO2Selectivity is>98％。
The catalyst is a noble metal catalyst and contains one or more active components of Pt, Pd, Ru, Rh, Ag and Ir, the cocatalyst is one or more of rare earth, alkali metal or alkaline earth metal oxides which are combined in any proportion, and the carrier is alumina balls, silica balls, titanium dioxide, molecular sieves, active carbon or carbon nano tubes and the like.
As shown in figure 1, the propylene gas catalytic deoxidation device with temperature and tail oxygen concentration control comprises a heat exchanger 1, an electric heater 2, a deoxidation reactor 3, an air condenser 4, a gas-liquid separation tank 5, a compressor 6 and a non-condensable gas separation tower 7, wherein the heat exchanger is provided with a first inlet, a second inlet, a first outlet and a second outlet, the first inlet is opposite to the first outlet, the first inlet is connected with a first inlet pipeline, and the first inlet pipeline is used for feeding raw material propylene tail gas into the heat exchanger; the outlet is connected with a first outlet pipeline; the other end of the first outlet pipeline is connected with the inlet end of the electric heater, and the outlet end of the electric heater is connected with the inlet end of the deoxygenation reactor; the outlet end of the deoxygenation reactor is connected with a second outlet pipeline, the other end of the second outlet pipeline is connected to the second inlet, a first temperature monitor is arranged on the second outlet pipeline, and the first temperature monitor is used for monitoring the temperature of gas discharged through the second outlet pipeline; a third outlet pipeline is connected to the second outlet, the third outlet pipeline is connected to the inlet end of the air condenser, the outlet end of the air condenser is connected to the inlet end of the gas-liquid separation tank, the gas-liquid separation tank is provided with a third outlet and a fourth outlet, the third outlet is used for discharging gas phase, the fourth outlet is used for discharging liquid phase, the third outlet is connected with a fourth outlet pipeline, a fourth outlet branch pipeline is arranged on the fourth outlet pipeline, the other end of the fourth outlet branch pipeline is connected to the first inlet pipeline, and the fourth outlet branch pipeline is used for sending the discharged excessive tail oxygen into the heat exchanger for treatment; a tail oxygen analyzer is arranged on the fourth outlet pipeline, and a second temperature monitor is arranged on the electric heater; the other end of the fourth outlet pipeline is connected with the inlet end of the compressor, the outlet end of the compressor is connected with the inlet end of the separation tower, the separation tower is provided with an outlet five and an outlet six, the outlet five is used for discharging gas phase, and the outlet six is used for discharging liquid phase.
The deoxidation process flow of the invention is briefly described as follows:
the method comprises the following steps of after heat exchange of raw material propylene tail gas by a heat exchanger, further heating the raw material propylene tail gas to a reaction operation temperature by an electric heater, entering a deoxygenation reactor, after heat exchange of gas after deoxygenation reaction and raw material gas, cooling the gas to 20 ℃ by an air condenser, entering a gas-liquid separation tank, separating a liquid phase generated in the reaction process, boosting the gas phase by a compressor, entering a non-condensable gas separation tower, separating the non-condensable gas from the gas phase, and obtaining pure propylene from the liquid phase.
Aiming at the problems of bed temperature runaway, excessive tail oxygen content and the like possibly caused by oxygen content fluctuation, catalyst activity reduction and the like in the olefin deoxidation process, two control loops are designed: the temperature of the outlet of the reactor and the temperature of the reaction inlet are controlled by tail gas circulation to control the oxygen content of the reaction tail gas.
Reactor outlet temperature control: after the temperature of the outlet of the reactor reaches 550 ℃, a reflux regulating valve is opened, and 10% of gas is controlled to reflux; when the temperature reaches 560 ℃, the reflux regulating valve is opened, and 15% of gas is controlled to reflux; when the temperature reaches 570 ℃, the reflux regulating valve is opened, and 20% of gas is controlled to reflux; when the temperature reaches 580 ℃, a reflux regulating valve is opened, and 30% of gas is controlled to reflux; when the temperature reaches 590 ℃, a reflux regulating valve is opened, and 40% of gas is controlled to reflux; when the temperature reaches 600 ℃, a reflux regulating valve is opened, and 50% of gas is controlled to reflux; the temperature is lower than 500 ℃, and the reflux is cut off.
Controlling the oxygen content of reaction tail gas: oxygen content of tail gas of CO2，CO2>After 0.15%, CO2Controlling the inlet temperature of the reactor to increase by 10 ℃ every 0.02% of the difference value of the temperature and the temperature of the outlet of the reactor to 0.15% until the inlet temperature of the reactor reaches 430 ℃ or the outlet temperature of the reactor reaches 600 ℃; cO2<After 0.1%, the reaction inlet temperature was controlled to decrease by 10 ℃.
The present invention will be described in detail with reference to specific examples.
Example 1:
the composition of the propylene tail gas is as follows: the oxygen volume percentage concentration is 5%; the concentration of propylene in percentage by volume is 90% and that of nitrogen is 5%. The reaction pressure is 1MPa, and the reaction space velocity is 10000hr-1. The propylene tail gas is subjected to heat exchange by a heat exchanger to 80 ℃, and then enters a deoxygenation reactor, wherein the outlet temperature of a reaction bed layer is 280 ℃. And exchanging heat between the gas after the deoxidation reaction and the feed gas to 80 ℃, cooling to 20 ℃ by an air condenser, and then feeding the gas into a gas-liquid separation tank to separate a liquid phase generated in the reaction process. The gas phase oxygen content was 0.1%, gradually increased to 0.17% during operation, and after increasing the reaction inlet temperature to 130 ℃, the gas phase oxygen content was brought to 0.14%, and operation was maintained under this operating condition.
Example 2:
the composition of the propylene tail gas is as follows: the oxygen volume percentage concentration is 3.5%; the concentration of propylene in percentage by volume is 90%, and the concentration of nitrogen is 6.5%. Reaction pressure of 3MPa and reaction space velocity of 30000hr-1. The propylene tail gas is subjected to heat exchange at 40 ℃ by a heat exchanger to 380 ℃, and then enters a deoxygenation reactor, wherein the outlet temperature of a reaction bed layer is 535 ℃. And exchanging heat between the gas after the deoxidation reaction and the feed gas to 120 ℃, cooling to 20 ℃ by an air 4 condenser, and then feeding the cooled gas into a gas-liquid separation tank to separate a liquid phase generated in the reaction process. The content of gas-phase oxygen is 0.18 percent, the temperature of a reaction inlet is increased to 390 ℃, the temperature of a reaction bed outlet is increased to 545 ℃, and the content of gas-phase oxygen is reduced to 0.16 percent; the temperature of the reaction inlet is continuously increased to 400 ℃, the temperature of the reaction bed outlet is increased to 555 ℃, the content of gas-phase oxygen is reduced to 0.12%, the temperature of the reactor outlet is controlled to be started, the reflux regulating valve is opened, 10% of gas is controlled to reflux, the temperature of the reactor outlet is reduced to 540 ℃, the content of gas-phase oxygen is 0.13%, and the operation is maintained under the operation condition.
Example 3:
the composition of the propylene tail gas is as follows: the oxygen volume percentage concentration is 4.6%; the concentration of propylene in percentage by volume is 90% and the nitrogen is 5.4%. Reaction pressure of 3MPa and reaction space velocity of 30000hr-1. The propylene tail gas is heated to 385 ℃ by the heat exchanger, and then enters a deoxygenation reactor, wherein the outlet temperature of a reaction bed layer is 595 ℃. Exchanging heat between the gas after the deoxidation reaction and the feed gas to 130 ℃, cooling to 20 ℃ by an air condenser, then feeding the gas into a gas-liquid separation tank, separating out a liquid phase generated in the reaction process, wherein the content of gas-phase oxygen is 0.11%, controlling the temperature of an outlet of the reactor to start, opening a reflux adjusting valve, controlling 40% of gas to reflux, controlling the temperature of the outlet of the reactor to 520 ℃ and the content of the gas-phase oxygen to 0.19%; adjusting the reaction temperature to 540 ℃, and adjusting the gas-phase oxygen content to 0.12%; operation was maintained under this operating condition.
Example 4:
the composition of the propylene tail gas is as follows: the oxygen volume percentage concentration is 1%; the concentration of propylene in volume percent was 96%, and the nitrogen was 4%. The reaction pressure is 2MPa, and the reaction space velocity is 40000hr-1. The propylene tail gas is subjected to heat exchange by a heat exchanger to 200 ℃, enters a deoxygenation reactor and is reactedThe bed outlet temperature should be 245 ℃. And exchanging heat between the gas after the deoxidation reaction and the feed gas to 75 ℃, cooling to 20 ℃ by an air condenser, and then feeding the gas into a gas-liquid separation tank to separate a liquid phase generated in the reaction process. The gas phase oxygen content was 0.20%, after increasing the reaction inlet temperature to 220 ℃, the gas phase oxygen content was brought to 0.09%, and operation was maintained under this operating condition.
The parts which are not described in the invention can be realized by taking the prior art as reference.
It is intended that any equivalents, or obvious variations, which may be made by those skilled in the art in light of the teachings herein, be within the scope of the present invention.
Claims (4)
1. A catalytic deoxidation method for propylene gas with temperature and tail oxygen concentration control is characterized in that: it adopts a propylene gas catalytic deoxidation device,
the propylene gas catalytic deoxidation device comprises a heat exchanger, an electric heater, a deoxidation reactor, an air condenser, a gas-liquid separation tank, a compressor and a separation tower, and is characterized in that: the heat exchanger is provided with a first inlet, a second inlet, a first outlet and a second outlet, the first inlet is opposite to the second outlet, the first inlet is connected with a first inlet pipeline, and the first inlet pipeline is used for feeding raw material propylene tail gas into the heat exchanger; the outlet is connected with a first outlet pipeline;
the other end of the first outlet pipeline is connected with the inlet end of the electric heater, and the outlet end of the electric heater is connected with the inlet end of the deoxygenation reactor;
the outlet end of the deoxygenation reactor is connected with a second outlet pipeline, the other end of the second outlet pipeline is connected to the second inlet, a first temperature monitor is arranged on the second outlet pipeline, and the first temperature monitor is used for monitoring the temperature of gas discharged through the second outlet pipeline;
the second outlet is connected with a third outlet pipeline, the third outlet pipeline is connected with the inlet end of the air condenser, the outlet end of the air condenser is connected with the inlet end of the gas-liquid separation tank, the gas-liquid separation tank is provided with a third outlet and a fourth outlet, the third outlet is used for discharging gas phase, the fourth outlet is used for discharging liquid phase, the third outlet is connected with a fourth outlet pipeline, a fourth outlet branch pipeline is arranged on the fourth outlet pipeline, the other end of the fourth outlet branch pipeline is connected with the first inlet pipeline, and the fourth outlet branch pipeline is used for sending the discharged overproof tail oxygen gas into the heat exchanger to be refluxed for treatment;
a tail oxygen analyzer is arranged on the fourth outlet pipeline, and a second temperature monitor is arranged on the electric heater;
the other end of the fourth outlet pipeline is connected with the inlet end of the compressor, the outlet end of the compressor is connected with the inlet end of the separation tower, the separation tower is provided with an outlet five and an outlet six, the outlet five is used for discharging gas phase, the outlet six is used for discharging liquid phase,
wherein a catalyst bed layer is arranged in the deoxygenation reactor, the catalyst selected by the catalyst bed layer comprises a main catalyst and an auxiliary catalyst, the main catalyst is a noble metal catalyst, the auxiliary catalyst is one or a mixture of more of rare earth, alkali metal or alkaline earth metal oxide,
the deoxidation method comprises the following steps:
a, propylene gas enters a heat exchanger through a first inlet pipeline, is discharged from a first outlet after being subjected to heat exchange by the heat exchanger, and enters the electric heater through a first outlet pipeline;
the propylene gas comprises the following components in percentage by volume: 0.5 to 8 percent of oxygen, 20 to 95 percent of propylene and the balance of nitrogen, carbon dioxide and hydrogen;
b, heating the mixture to a temperature required by the reaction by an electric heater, and reacting the mixture in a deoxygenation reactor, wherein the operating pressure in the deoxygenation reactor is 1-3 MPa, and the reaction operating temperature is 100-430 ℃;
c, discharging the gas after the deoxidation reaction through a second outlet pipeline, measuring the temperature of the discharged gas through a first temperature monitor, feeding the gas after the deoxidation reaction into the heat exchanger, exchanging heat with the feed gas, cooling through an air condenser, feeding the gas into the gas-liquid separation tank, and separating a liquid phase generated in the reaction process through an outlet;
d, separating out gas phase through an outlet, analyzing the tail oxygen content through a tail oxygen analyzer, controlling gas reflux through a valve on a fourth branch pipeline when the tail oxygen content is more than or equal to 0.15 percent, cutting off reflux when the tail oxygen content is less than 0.15 percent, boosting the pressure of the gas phase through a compressor, then feeding the gas phase into a separation tower, separating out noncondensable gas through the gas phase, obtaining pure propylene through a liquid phase,
the gas phase reflux amount is controlled by the temperature measured by the first temperature monitor,
when the temperature measured by the first temperature monitor is greater than or equal to 550 ℃ and less than 560 ℃, controlling 10% of gas to flow back; when the temperature measured by the first temperature monitor is higher than or equal to 560 ℃ and lower than 570 ℃, controlling 15% of gas reflux; when the temperature measured by the first temperature monitor is greater than or equal to 570 ℃ and less than 580 ℃, controlling 20% of gas to flow back; when the temperature measured by the first temperature monitor is greater than or equal to 580 ℃ and less than 590 ℃, controlling 30% of gas reflux; when the temperature measured by the first temperature monitor is greater than or equal to 590 ℃ and less than 600 ℃, controlling 40% of gas reflux; when the temperature measured by the first temperature monitor is more than or equal to 600 ℃, 50 percent of gas reflux is controlled.
2. The catalytic deoxygenation method of claim 1, wherein the catalytic deoxygenation method comprises the following steps: the outlet temperature of the catalyst bed layer is 200-600 ℃, and the space velocity of the propylene gas in the catalyst bed layer is 500-50000hr-1。
3. The catalytic deoxygenation method of claim 1, wherein the catalytic deoxygenation method comprises the following steps: the noble metal catalyst contains one or more active components of Pt, Pd, Ru, Rh, Ag and Ir.
4. The catalytic deoxygenation method of claim 3 for propylene gas with temperature and tail oxygen concentration control, comprising the following steps: the carrier selected by the catalyst is alumina ball, silicon dioxide ball, titanium dioxide, molecular sieve, active carbon or carbon nano tube.
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