CN210796285U - Device and system for preparing olefin through reaction of carbon dioxide and low-carbon alkane - Google Patents
Device and system for preparing olefin through reaction of carbon dioxide and low-carbon alkane Download PDFInfo
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- CN210796285U CN210796285U CN201921802613.1U CN201921802613U CN210796285U CN 210796285 U CN210796285 U CN 210796285U CN 201921802613 U CN201921802613 U CN 201921802613U CN 210796285 U CN210796285 U CN 210796285U
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Abstract
The utility model provides a device and a system for preparing olefin by the reaction of carbon dioxide and low-carbon alkane, the device for preparing olefin by the reaction of carbon dioxide and low-carbon alkane comprises a feed inlet, a feed preheating furnace and a reaction furnace, the feed inlet is connected with the inlet of the feed preheating furnace, the outlet of the feed preheating furnace is connected with the inlet of the reaction furnace, and the inlet of the reaction furnace is provided with a first gas distributor; the reaction furnace comprises a reaction furnace shell, wherein a plurality of layers of heating areas are arranged in the reaction furnace shell, and the heating areas are surrounded by a first heating wall; a plurality of rows of reaction tubes are arranged in each heating area in parallel, one end of each reaction tube is connected with the first gas distributor, and the other end of each reaction tube is connected with an outlet of the reaction furnace; a plurality of first heating nozzles are arranged between the reaction tubes. In the device and the system for preparing the olefin by the reaction of the carbon dioxide and the low-carbon alkane, the temperature distribution of the reaction device is uniform, the temperature is easy to control, and the reaction system effectively utilizes waste heat and waste materials generated in each step, thereby reducing the waste of energy and raw materials.
Description
Technical Field
The utility model belongs to the technical field of the conversion and the utilization of carbon dioxide, concretely relates to device and system of carbon dioxide and low carbon alkane reaction system alkene.
Background
With the development of modern industry, the global energy consumption is increasing dramatically, the emission of carbon dioxide is from 0.4 million tons before the industrial revolution to 60.4 million tons in 1996, and the total emission of carbon dioxide is estimated to increase to 360 million tons in 2100 years. The increasing amount of carbon dioxide with the development of industry has increased the deterioration of human living environment, and the gradual reduction of greenhouse gas emission has become a consensus of most scientists and government agencies.
Carbon dioxide is used as an important chemical raw material, and can be converted into products with higher economic value, such as white carbon black, borax, light magnesium oxide, propylene carbonate, salicylic acid, cyano-muscle and the like through chemical processing. The application can provide important industrial raw material olefin, can eliminate carbon dioxide causing greenhouse effect, and is a catalytic reaction with industrial application prospect. At present, most of the structures of the constant-temperature reaction furnaces applied to the industry are integral cylindrical reaction tubes, the heating furnace heats the outer wall of the reaction tubes, reaction gas enters the reaction tubes to perform constant-temperature reaction, but the yield is high for industrial production, the tube diameters of the reaction tubes are large, the reaction tubes are limited by heat transfer conditions, the temperatures of different positions in the reaction tubes are not uniform, and the reaction temperature is not easy to control. For the process of preparing products such as olefin by the reaction of carbon dioxide and low-carbon alkane, the process only involves the simple separation of the reaction and the products in the industry, the purity of the obtained olefin is not high, and waste heat and waste materials generated in each step of treatment are not effectively utilized, so that the waste of energy and raw materials is caused.
SUMMERY OF THE UTILITY MODEL
The utility model provides a technical problem provide a device and system of carbon dioxide and low carbon alkane reaction system alkene, temperature distribution homogeneous in reaction unit, the temperature is easily controlled, and reaction system is effectual to have utilized the used heat and the waste material that each step produced, and it is extravagant to reduce energy, raw materials.
In order to solve the problems, the utility model provides a device for preparing olefin by reacting carbon dioxide with low-carbon alkane, which comprises a feed inlet, a feed preheating furnace and a reaction furnace, wherein the feed inlet is connected with an inlet of the feed preheating furnace, an outlet of the feed preheating furnace is connected with an inlet of the reaction furnace, and an inlet of the reaction furnace is provided with a first gas distributor; the reaction furnace comprises a reaction furnace shell, wherein a plurality of layers of heating areas are arranged in the reaction furnace shell, and the heating areas are surrounded by a first heating wall; a plurality of rows of reaction tubes are arranged in each heating area in parallel, one end of each reaction tube is connected with the first gas distributor, and the other end of each reaction tube is connected with an outlet of the reaction furnace; a first heating nozzle is arranged between the reaction tubes.
Preferably, the system also comprises a first waste heat exchange device, wherein the first waste heat exchange device comprises a tube side and a shell side; an outlet of the reaction furnace is connected with a tube pass inlet of the first waste heat exchange device, and a tube pass outlet of the first waste heat exchange device is connected with a discharge hole; the feed inlet is connected with a shell pass inlet of the first waste heat exchange device, and a shell pass outlet of the first waste heat exchange device is connected with an inlet of the feed preheating furnace.
Preferably, the feed preheater comprises a preheater housing; a second heating wall is arranged on the inner wall of the preheating furnace shell; a second gas distributor is arranged at the inlet of the feeding preheating furnace; a plurality of rows of preheating pipes are arranged in parallel in the preheating furnace shell, one end of each preheating pipe is connected with the second gas distributor, and the other end of each preheating pipe is connected with an outlet of the feeding preheating furnace; a plurality of second heating nozzles are arranged between the preheating pipes.
Preferably, the waste heat recovery device further comprises a feeding buffer tank, the feeding port comprises a carbon dioxide feeding port and a low-carbon alkane feeding port, the carbon dioxide feeding port and the low-carbon alkane feeding port are respectively connected with an inlet of the feeding buffer tank, and an outlet of the feeding buffer tank is connected with a shell pass inlet of the first waste heat exchange device.
Preferably, the system also comprises a feeding mixer suitable for mixing carbon dioxide, low-carbon alkane and water vapor, wherein the feeding mixer is provided with a water vapor inlet, the inlet of the feeding mixer is connected with the outlet of the feeding preheating furnace, and the outlet of the feeding mixer is connected with the inlet of the reaction furnace.
Another objective of the present invention is to provide a system for producing olefins by reacting carbon dioxide with light alkanes, which comprises the above apparatus for producing olefins by reacting carbon dioxide with light alkanes, the apparatus for producing olefins by reacting carbon dioxide with light alkanes further comprises a first waste heat exchanger, a second waste heat exchanger and a quenching device; a hot medium inlet of the first waste heat exchange device is connected with an outlet of the reaction furnace, a hot medium outlet of the first waste heat exchange device is connected with a hot medium inlet of the second waste heat exchange device, a cold medium inlet of the first waste heat exchange device is connected with the feed inlet, and a cold medium outlet of the first waste heat exchange device is connected with an inlet of the feeding preheating furnace; and a heat medium outlet of the second waste heat exchange device is connected with a heat medium inlet of the quenching device, and a heat medium outlet of the quenching device is connected with a discharge hole.
Preferably, the device for preparing olefin by reacting carbon dioxide with low-carbon alkane further comprises a fourth gas-liquid separator and a filter, wherein the outlet of the heat medium of the quenching device is connected with the fourth gas-liquid separator, the gas-phase outlet of the fourth gas-liquid separator is connected with the discharge hole, and the liquid-phase outlet of the fourth gas-liquid separator is connected with the filter.
Preferably, the system also comprises a crude separation unit, wherein the crude separation unit comprises a decarburization absorption tower, an alkaline washing tower, a first cooler, a first gas-liquid separator, a regeneration tower, a benzene washing tower and a dryer; a hot medium outlet of the quenching device is connected with a gas phase inlet of the decarburization absorption tower, a gas phase outlet of the decarburization absorption tower is connected with a gas phase inlet of the alkaline washing tower, a gas phase outlet of the alkaline washing tower is connected with a first cooler, the first cooler is connected with a first gas-liquid separator, a gas phase outlet of the first gas-liquid separator is connected with a gas phase inlet of the benzene washing tower, a gas phase outlet of the benzene washing tower is connected with an inlet of a dryer, and an outlet of the dryer is connected with a discharge hole; the liquid phase outlet of the decarburization absorption tower is connected with the liquid phase inlet of the regeneration tower, the gas phase outlet of the regeneration tower is connected with the feed inlet, and the liquid phase outlet of the regeneration tower is connected with the liquid phase inlet of the decarburization absorption tower.
Preferably, the coarse separation unit further comprises a first gas compressor, the gas-phase outlet of the fourth gas-liquid separator is connected to the inlet of the first gas compressor, and the outlet of the first gas compressor is connected to the gas-phase inlet of the decarburization absorption tower.
Preferably, the coarse separation unit further comprises a first reflux tank, an air cooler and an aftercooler, the gas-phase outlet of the regeneration tower is connected with the inlet of the air cooler, the outlet of the air cooler is connected with the inlet of the aftercooler, the outlet of the aftercooler is connected with the inlet of the first reflux tank, the liquid-phase outlet of the first reflux tank is connected with the reflux inlet of the regeneration tower, and the gas-phase outlet of the first reflux tank is connected with the feed inlet.
Preferably, the rough separation unit further comprises a first heat exchange device, a heat medium inlet of the first heat exchange device is connected with the liquid phase outlet of the regeneration tower, a heat medium outlet of the first heat exchange device is connected with the liquid phase inlet of the decarburization absorption tower, a cold medium inlet of the first heat exchange device is connected with the liquid phase outlet of the decarburization absorption tower, and a cold medium outlet of the first heat exchange device is connected with the liquid phase inlet of the regeneration tower.
Preferably, the dryer includes first desicator and second desicator, and the gaseous phase export of washing the benzene tower is connected with first desicator and second desicator respectively through first pipeline and second pipeline, and the nitrogen supply device is connected with first desicator and second desicator respectively through third pipeline and fourth pipeline, all is equipped with the control valve on first pipeline, second pipeline, third pipeline, the fourth pipeline.
Preferably, the system also comprises a fine separation unit, wherein the fine separation unit comprises a second cooler, a second gas-liquid separator, a third cooler, a third gas-liquid separator, a first paraffin removal tower, a hydrogenation device, an olefin separation tower, an olefin collection device and a second paraffin removal tower; an outlet of the dryer is connected with the second cooler, the second cooler is connected with the second gas-liquid separator, a gas-phase outlet of the second gas-liquid separator is connected with the third cooler, the third cooler is connected with the third gas-liquid separator, a liquid-phase outlet of the third gas-liquid separator is connected with a liquid-phase inlet of the first dealkylation tower, a gas-phase outlet of the third gas-liquid separator is connected with the synthesis gas separation unit, a gas-phase outlet of the first dealkylation tower is connected with the synthesis gas separation unit, a liquid-phase outlet of the first dealkylation tower is connected with an inlet of the hydrogenation device, an outlet of the hydrogenation device is connected with a liquid-phase inlet of the olefin separation tower, a gas-phase outlet of the olefin separation tower is connected with the olefin collection device, a liquid-phase outlet of the olefin separation tower is connected with a liquid-phase inlet of the second dealkylation tower, a gas-phase outlet of the second dealkylation tower is connected with the feed inlet, and.
Preferably, the fine separation unit further comprises a second gas compressor, the outlet of the dryer is connected with the inlet of the second gas compressor, and the outlet of the second gas compressor is connected with the second cooler.
Preferably, the fine separation unit further comprises a second heat exchange device, a heat medium inlet of the second heat exchange device is connected with an outlet of the second gas compressor, and a heat medium outlet of the second heat exchange device is connected with the second cooler; the cold medium inlet of the second heat exchange device is connected with the liquid phase outlet of the first dealkylation tower, and the cold medium outlet of the second heat exchange device is connected with the inlet of the hydrogenation device.
Preferably, the fine separation unit further comprises a fifth cooler and a fifth gas-liquid separator, the gas phase outlet of the first paraffin removal tower is connected with the fifth cooler, the fifth cooler is connected with the fifth gas-liquid separator, the liquid phase outlet of the fifth gas-liquid separator is connected with the reflux inlet of the first paraffin removal tower, and the gas phase outlet of the fifth gas-liquid separator is connected with the synthesis gas separation unit.
Preferably, the synthesis gas separation unit comprises a pressure swing adsorption device and a hydrogen collection device, a gas phase outlet of the third gas-liquid separator and a gas phase outlet of the first dealkylation tower are connected with an inlet of the pressure swing adsorption device, the pressure swing adsorption device is connected with the hydrogen collection device, and the hydrogen collection device is connected with an inlet of the hydrogenation device.
The lower alkane means an alkane having 4 or less carbon atoms and includes methane, ethane, propane and butane.
Compared with the prior art, the utility model, following beneficial effect has:
1. carbon dioxide and low carbon alkane react device of system alkene, divide into the stranded feed gas in the reacting furnace and send to each reaction tube respectively, divide the reaction zone into a plurality of reaction tubes, and set up the heating nozzle between adjacent reaction tube, the heating nozzle spouts fuel or gas, heat the reaction tube through the burning, can make the heat transfer of the feed gas in the reaction zone change into the heat transfer that inside and outside goes on simultaneously by inhomogeneous outside-in's heat transfer, make the feed gas heat transfer more even, stable, feed gas reaction temperature is changeed and is controlled, temperature control is also more accurate; in addition, the reaction temperature in different heating areas can be controlled according to requirements, and reaction process parameters in different heating areas can be regulated and controlled, so that the product distribution can be regulated and the energy consumption can be reduced;
2. the device for preparing olefin by reacting carbon dioxide with low-carbon alkane, disclosed by the utility model, has the advantages that through the arrangement of the first waste heat exchange device, high-temperature process gas generated by the reaction furnace exchanges heat with low-temperature raw gas in the shell pass of the first waste heat exchange device in the tube pass of the first waste heat exchange device, so that the temperature of the raw gas is preliminarily improved, the energy consumption of the feeding preheating furnace can be saved, the waste heat of product gas is effectively utilized, and the energy waste is avoided;
3. the utility model discloses a device for preparing alkene by carbon dioxide and low carbon alkane reaction, set up the gas distributor at the feeding preheater to set up multirow preheating tube in the feeding preheater, evenly divide into a plurality of strands through the gas distributor with the mixed feed gas that gets into, get into solitary preheating tube, then get into corresponding reaction tube, can make the feed gas evenly distributed in advance on the one hand, guarantee that the feed gas is by even equivalent distribution into different reaction tubes; on the other hand, by arranging a plurality of preheating pipes, the raw material gas heating area is divided into a plurality of preheating pipes, a heating nozzle is arranged between the adjacent preheating pipes, fuel oil or fuel gas is sprayed into the heating nozzle, and the reaction pipes are heated by combustion, so that the heat transfer of the raw material gas in the preheating area is changed from inhomogeneous heat transfer from outside to inside into heat transfer which is carried out simultaneously from inside to outside, the preheating of the raw material gas is more uniform and stable, the preheating temperature is easier to control, and the temperature control is more accurate;
4. the utility model discloses a system for carbon dioxide and low carbon alkane reaction system alkene, after carbon dioxide, water and low carbon alkane reaction, through cooling, decarbonization, debenzolization, drying, once take off alkane, hydrogenation, alkene separation, secondary take off alkane, finally obtained alkene product and synthetic gas, wherein, all effectively utilized the waste heat in the process step, and the by-product that produces in each step also all is used as absorbent, detergent or heat source, has practiced thrift raw materials and energy greatly; the separated unreacted low-carbon alkane and carbon dioxide are sent to the feeding hole for recycling, so that the consumption of raw materials is reduced, the utilization rate of energy is improved, the air pollution caused by redundant low-carbon alkane and carbon dioxide is avoided, and the recycling of the raw materials and the energy is realized;
5. the utility model discloses a system for carbon dioxide and low carbon alkane reaction system alkene still can be according to the required raw materials composition of low reaches production technology, regulates and control the result through the proportion of adjusting raw materials carbon dioxide, water, low carbon alkane and distributes to adapt to the demand of low reaches technology to the raw materials proportion.
Drawings
FIG. 1 is a front view of an apparatus for producing olefins by reacting carbon dioxide with light alkanes according to a first embodiment of the present invention;
FIG. 2 is a top view of an apparatus for producing olefins by reacting carbon dioxide with light alkanes according to a first embodiment of the present invention;
fig. 3 is a schematic structural diagram of a system for producing olefins by reacting carbon dioxide with light alkanes according to an embodiment of the present invention.
Wherein: 1-a feed inlet; 2-a feed preheater; 3-a reaction furnace; 4-a first waste heat exchange device; 5-a feed buffer tank; 6-a feeding mixer; 7-a second waste heat exchange device; 8-a quenching device; 9-a fourth gas-liquid separator; 10-a filter; 11-carbon dioxide feed inlet; 12-lower alkane feed inlet; 13-a decarbonization absorption tower; 14-an alkaline washing tower; 15-a first cooler; 16-a first gas-liquid separator; 17-a regeneration column; 18-a benzene washing tower; 19-a dryer; 20-a first gas compressor; 21-preheating a furnace shell; 22-a second heating wall; 23-a preheating pipe; 24-a second heating nozzle; 25-a first reflux drum; 26-an air cooler; 27-aftercooler; 28-first heat exchange means; 29-a second cooler; 30-a second gas-liquid separator; 31-a reactor shell; 32-a first heating wall; 33-a reaction tube; 34-a first heating nozzle; 35-a third cooler; 36-a third gas-liquid separator; 37-a first dealkylation column; 38-a hydrogenation unit; a 39-olefin separation column; a 40-olefin collection device; 41-tube pass; 42-shell side; 43-a second dealkylation column; 44-a second gas compressor; 45-second heat exchange means; 46-a fifth cooler; 47-fifth gas-liquid separator; 48-pressure swing adsorption device.
Detailed Description
The technical solution of the present invention will be described clearly and completely below with reference to the embodiments of the present invention, and it should be understood that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
Example one
As shown in fig. 1 and 2, the apparatus for preparing olefin by reacting carbon dioxide with light alkane described in this embodiment includes a feeding port 1, a feeding preheating furnace 2 and a reaction furnace 3, the feeding port 1 is connected to an inlet of the feeding preheating furnace 2, an outlet of the feeding preheating furnace 2 is connected to an inlet of the reaction furnace 3, and an inlet of the reaction furnace 3 is provided with a first gas distributor; the reaction furnace 3 comprises a reaction furnace shell 31, wherein a plurality of heating areas are arranged in the reaction furnace shell 31, and the heating areas are surrounded by a first heating wall 32; a plurality of rows of reaction tubes 33 are arranged in each heating area in parallel, one end of each reaction tube 33 is connected with the first gas distributor, and the other end is connected with the outlet of the reaction tube; the first heating nozzle 34 is provided between the reaction tubes 33.
Carbon dioxide and low-carbon alkane are fed through a feeding hole 1, enter a feeding preheating furnace 2 to be preheated preliminarily, and are then fed into a reaction furnace 3, the mixed reaction raw material gas is distributed into a plurality of reaction tubes in the reaction furnace by a first gas distributor, alkane dehydrogenation catalysts are filled in the reaction tubes, the reaction tubes are heated to the reaction temperature by heating of a first heating wall 32 and a first heating nozzle 34 arranged in each heating area, and the dehydrogenation reforming reaction of the low-carbon alkane is carried out, so that the products of alkene, carbon monoxide, hydrogen and the like are obtained. The raw material gas in the reaction furnace is divided into a plurality of strands and is respectively sent to each reaction tube, the reaction area is divided into a plurality of reaction tubes, and the heating furnace wires are arranged between the adjacent reaction tubes, so that the heat transfer of the raw material gas in the reaction area is changed from non-uniform heat transfer from outside to inside into heat transfer which is carried out simultaneously from inside to outside, the heat transfer of the raw material gas is more uniform and stable, the reaction temperature of the raw material gas is easier to control, and the temperature control is more accurate; in addition, the reaction temperature in different heating areas can be controlled according to requirements, the type of the catalyst filled in the reaction tubes in different areas can be controlled, for example, the temperature of the heating area close to the feed inlet can be controlled to be 600 ℃, the heating temperature is increased to 700 ℃ and 800 ℃ along with the flow direction of the raw material gas, the temperature of the final heating area is ensured to be 900 ℃, and energy can be greatly saved under the condition of ensuring the conversion rate of the final product.
Further, the heat recovery device also comprises a first waste heat exchange device 4, wherein the first waste heat exchange device 4 comprises a tube pass 41 and a shell pass 42; an outlet of the reaction furnace 3 is connected with an inlet of a tube side 41 of the first waste heat exchange device 4, and an outlet of the tube side 41 of the first waste heat exchange device 4 is connected with a discharge hole; the feed inlet 1 is connected with the inlet of the shell pass 42 of the first waste heat exchange device 4, and the outlet of the shell pass 42 of the first waste heat exchange device 4 is connected with the inlet of the feed preheating furnace 2. High-temperature process gas generated by the reaction furnace exchanges heat with low-temperature raw gas in a shell pass 42 of the first waste heat exchange device 4 in a tube pass 41 of the first waste heat exchange device 4, so that the temperature of the raw gas is preliminarily improved, the energy consumption of the feeding preheating furnace 2 can be saved, the waste heat of product gas is effectively utilized, and the energy waste is avoided.
Further, the feed preheater 2 includes a preheater housing 21; the inner wall of the preheating furnace shell 21 is provided with a second heating wall 22; a second gas distributor is arranged at the inlet of the feeding preheating furnace 2; a plurality of rows of preheating pipes 23 are arranged in the preheating furnace shell 21 in parallel, one end of each preheating pipe 23 is connected with the second gas distributor, and the other end of each preheating pipe 23 is connected with an outlet of the feeding preheating furnace 2; a second heating nozzle 24 is arranged between the preheating pipes 23. The gas distributor uniformly divides the entering mixed raw material gas into a plurality of strands, and the strands enter the corresponding reaction tubes, so that on one hand, the raw material gas can be uniformly distributed in advance, and the raw material gas is guaranteed to be uniformly and equivalently distributed into different reaction tubes; on the other hand, the plurality of preheating pipes are arranged, so that the raw material gas heating area is divided into the plurality of preheating pipes, and the heating furnace wires are arranged between the adjacent preheating pipes, so that the heat transfer of the raw material gas in the preheating area is changed from inhomogeneous heat transfer from outside to inside into heat transfer which is carried out simultaneously from inside to outside, the preheating of the raw material gas is more uniform and stable, the preheating temperature is easier to control, and the temperature control is more accurate.
Further, the waste heat recovery device further comprises a feeding buffer tank 5, the feeding port 1 comprises a carbon dioxide feeding port 11 and a low-carbon alkane feeding port 12, the carbon dioxide feeding port 11 and the low-carbon alkane feeding port 12 are respectively connected with an inlet of the feeding buffer tank 5, and an outlet of the feeding buffer tank 5 is connected with an inlet of a shell pass 42 of the first waste heat exchange device 4. The feed gas carbon dioxide and the low-carbon alkane entering from the feed inlet firstly enter the feed buffer tank to be mixed, and the uniformly mixed feed gas enters the first waste heat exchange device to perform preliminary heat exchange, so that the two gases in the feed gas entering the reaction tube are uniformly mixed, and the proportion is closer to the preset mixing proportion.
Example two
The apparatus for preparing olefin by reacting carbon dioxide with low carbon alkane described in this embodiment is obtained by further improving the apparatus for preparing olefin by reacting carbon dioxide with low carbon alkane in the first embodiment, and the structure of the rest of the apparatus is the same as that in the first embodiment, except that the apparatus for preparing olefin by reacting carbon dioxide with low carbon alkane in this embodiment further comprises a feeding mixer 6 suitable for mixing carbon dioxide, low carbon alkane and water vapor, the feeding mixer 6 is provided with a water vapor inlet, the inlet of the feeding mixer 6 is connected with the outlet of the feeding preheating furnace 2, and the outlet of the feeding mixer 6 is connected with the inlet of the reaction furnace 3. The mixed gas of the carbon dioxide and the low-carbon alkane preheated by the feeding preheating furnace 2 enters the feeding mixer 6, is mixed with the water vapor injected from the water vapor inlet, and then enters the reaction furnace for reaction. The water vapor is independently mixed with the mixed carbon dioxide and the low-carbon alkane, the addition amount of the water vapor can be more strictly and accurately controlled, the control proportion of the input amount of the raw materials is more accurate, and the regulation and control on the amount of the product are more accurate.
As shown in fig. 3, the system for producing olefins by reacting carbon dioxide with light alkanes of this embodiment includes the apparatus for producing olefins by reacting carbon dioxide with light alkanes, and in addition, the apparatus for producing olefins by reacting carbon dioxide with light alkanes further includes a second waste heat exchanger 7 and a quenching apparatus 8; a tube side inlet of the first waste heat exchange device 4 is connected with an outlet of the reaction furnace 3, a tube side outlet of the first waste heat exchange device 4 is connected with a heat medium inlet of the second waste heat exchange device 7, a shell side inlet of the first waste heat exchange device 4 is connected with the feed inlet 1, and a shell side outlet of the first waste heat exchange device 4 is connected with an inlet of the feed preheating furnace 2; the heat medium outlet of the second waste heat exchange device 7 is connected with the heat medium inlet of the quenching device 8, and the heat medium outlet of the quenching device 8 is connected with the discharge hole. High temperature process gas generated by reaction in the reaction furnace 3 enters the first waste heat exchange device 4 for heat exchange, is primarily cooled and effectively utilizes waste heat, then enters the second waste heat exchange device 7 for further cooling, and then enters the quenching device for cooling to a lower temperature for collection.
The first waste heat exchange device 4 can be a heat exchanger or a waste heat boiler, the second waste heat exchange device 7 can be a heat exchanger or a waste heat boiler, high-temperature process gas generated by the reaction furnace firstly enters the first waste heat boiler to generate 3-5 MPa-level saturated steam, the saturated steam can enter a flue of the reaction furnace to be overheated and serves as a compressor turbine or a heat source of the device, the high-temperature process gas is cooled to a certain temperature and then enters the second waste heat boiler to be further cooled, and the second waste heat boiler generates 0.3-0.5 MPa-level saturated steam and can serve as a heat source of any one or any plurality of devices in the system; the quench unit 8 may be a quench tower.
Further, the device for preparing olefin by reacting carbon dioxide with low-carbon alkane further comprises a fourth gas-liquid separator 9 and a filter 10, wherein a heat medium outlet of the quenching device 8 is connected with the fourth gas-liquid separator 9, a gas-phase outlet of the fourth gas-liquid separator 9 is connected with a discharge hole, and a liquid-phase outlet of the fourth gas-liquid separator 9 is connected with the filter. The process gas cooled by the quenching device enters a fourth gas-liquid separator 9 for gas-liquid separation, the separated gas product is collected, the liquid product enters a filter 10 for filtering out impurities such as coke generated by reaction, and then the liquid product can be used as a heat source of any one or more devices in the system.
Further, the system for preparing the olefin by the reaction of the carbon dioxide and the light alkane further comprises a coarse separation unit, wherein the coarse separation unit comprises a decarburization absorption tower 13, an alkaline washing tower 14, a first cooler 15, a first gas-liquid separator 16, a regeneration tower 17, a benzene washing tower 18 and a dryer 19; a gas phase outlet of a fourth gas-liquid separator 9 at a heat medium outlet of the quenching device 8 is connected with a gas phase inlet of a decarburization absorption tower 13, a gas phase outlet of the decarburization absorption tower 13 is connected with a gas phase inlet of an alkaline washing tower 14, a gas phase outlet of the alkaline washing tower 14 is connected with a first cooler 15, the first cooler 15 is connected with a first gas-liquid separator 16, a gas phase outlet of the first gas-liquid separator 16 is connected with a gas phase inlet of a benzene washing tower 18, a gas phase outlet of the benzene washing tower 18 is connected with an inlet of a dryer 19, and an outlet of the dryer 19 is connected with a discharge hole; the liquid phase outlet of the decarburization absorption tower 13 is connected with the liquid phase inlet of the regeneration tower 17, the gas phase outlet of the regeneration tower 17 is connected with the feed inlet 1, and the liquid phase outlet of the regeneration tower 17 is connected with the liquid phase inlet of the decarburization absorption tower 13. The crude separation unit can separate carbon dioxide, water vapor, benzene and the like in the product gas to remove impurity components in the product. The cooled gas product enters a decarburization absorption tower 13 to primarily remove carbon dioxide, then enters an alkaline tower 14 to remove trace carbon dioxide, then enters a first cooler 15 to be cooled, then is subjected to liquid separation in a first gas-liquid separator 16, the gas after liquid separation is introduced into a benzene washing tower 18 to remove benzene therein, and finally enters a dryer 19 to be dried, and water vapor is removed, so that the gas product with impurities primarily removed is obtained. Wherein, the absorbent in the decarburization absorption tower 13 enters the regeneration tower for regeneration after being absorbed and saturated.
Further, 20-40% MDEA solution is used as absorbent in the decarbonization absorption tower 13.
Further, the coarse separation unit further comprises a first gas compressor 20, the gas phase outlet of the fourth gas-liquid separator 9 is connected with the inlet of the first gas compressor 20, and the outlet of the first gas compressor 20 is connected with the gas phase inlet of the decarburization absorption tower 13. The gas obtained after cooling and liquid separation by the quenching device is sent to the first gas compressor 20 for pressurization, and then sent to the decarburization absorption tower 13 for decarburization treatment.
Preferably, the coarse separation unit further comprises a first reflux drum 25, an air cooler 26 and an aftercooler 27, the gas phase outlet of the regeneration tower 17 is connected with the inlet of the air cooler 26, the outlet of the air cooler 26 is connected with the inlet of the aftercooler 27, the outlet of the aftercooler 27 is connected with the inlet of the first reflux drum 25, the liquid phase outlet of the first reflux drum 25 is connected with the reflux inlet of the regeneration tower 17, and the gas phase outlet of the first reflux drum 25 is connected with the feed port 2. The tower top gas of the absorbent regeneration tower is primarily cooled by an air cooler 26, and then is further cooled by a post cooler 27, the liquid obtained by cooling flows back to the regeneration tower, the separated gas is carbon dioxide, and the carbon dioxide and the raw material carbon dioxide are mixed and then are used as the feeding material together.
Preferably, the coarse separation unit further comprises a first heat exchange device 28, the heat medium inlet of the first heat exchange device 28 is connected with the liquid phase outlet of the regeneration tower 17, the heat medium outlet of the first heat exchange device 28 is connected with the liquid phase inlet of the decarburization absorption tower 13, the cold medium inlet of the first heat exchange device 28 is connected with the liquid phase outlet of the decarburization absorption tower 13, and the cold medium outlet of the first heat exchange device 28 is connected with the liquid phase inlet of the regeneration tower 17. The barren solution at the tower bottom of the regeneration tower of the absorbent and the rich solution of the absorbent in the decarburization absorption tower carry out primary heat exchange in the first heat exchange device 28, the waste heat of the barren solution is fully utilized, and then the rich solution enters the regeneration tower for regeneration.
Preferably, the dryer 19 includes a first dryer and a second dryer, the gas phase outlet of the benzene washing tower is connected with the first dryer and the second dryer through a first pipeline and a second pipeline respectively, the nitrogen supply device is connected with the first dryer and the second dryer through a third pipeline and a fourth pipeline respectively, and the first pipeline, the second pipeline, the third pipeline and the fourth pipeline are all provided with control valves. And one dryer is controlled to be connected into the system by adjusting control valves on four pipelines to dry the product gas, and the other dryer is connected into a nitrogen supply device to blow in nitrogen and heat for regeneration. The two driers are used alternately, so that the production efficiency is improved.
Preferably, a fine separation unit is further included, the fine separation unit including a second cooler 29, a second gas-liquid separator 30, a third cooler 35, a third gas-liquid separator 36, a first de-alkane tower 37, a hydrogenation apparatus 38, an olefin separation tower 39, an olefin collection apparatus 40, and a second de-alkane tower 43; an outlet of the dryer 19 is connected with the second cooler 29, the second cooler 29 is connected with the second gas-liquid separator 30, a gas phase outlet of the second gas-liquid separator 30 is connected with the third cooler 35, the third cooler 35 is connected with the third gas-liquid separator 36, a liquid phase outlet of the third gas-liquid separator 36 is connected with a liquid phase inlet of the first dealkylation tower 37, a gas phase outlet of the third gas-liquid separator 36 is connected with the synthesis gas separation unit, a gas phase outlet of the first dealkylation tower 37 is connected with the synthesis gas separation unit, a liquid phase outlet of the first dealkylation tower 37 is connected with an inlet of the hydrogenation device 38, an outlet of the hydrogenation device 38 is connected with a liquid phase inlet of the alkene separation tower 39, a gas phase outlet of the alkene separation tower 39 is connected with the alkene collection device 40, a liquid phase outlet of the alkene separation tower 39 is connected with a liquid phase inlet of the second dealkylation tower 43, a gas phase outlet of the second dealkylation tower 43 is connected with, the liquid phase outlet of the second dealkylation column 43 is connected to the liquid phase inlet of the benzene scrubber 18. The product gas after the crude separation enters a second cooler 29 for cooling, then liquid is separated in a second gas-liquid separator 30, the gas product after the liquid separation enters a third cooler 35 for further cooling, then gas-liquid separation is carried out, the separated liquid enters a first dealkanization tower 37, and the separated gas is sent to a synthesis gas separation unit; after the separated liquid is separated into alkane by the first dealkylation tower, a small amount of alkyne is contained in the liquid phase at the bottom of the first dealkylation tower, the alkyne is introduced into a hydrogenation device for hydrogenation treatment, the alkyne is converted into alkene and alkane, the hydrogenated product enters an alkene separation tower, the product alkene is separated, the alkene in the gas phase at the top of the alkene separation tower is collected, the liquid phase at the bottom of the alkene separation tower enters a second dealkylation tower, the low-carbon alkane separated by the second dealkylation tower is mixed with the raw material low-carbon alkane to be used as a feed, and the liquid phase at the bottom of the second dealkylation tower is C3+ and is used as a washing agent of the benzene washing tower 18.
Preferably, the fine separation unit further comprises a second gas compressor 44, the outlet of the dryer 19 being connected to the inlet of the second gas compressor 44, the outlet of the second gas compressor 44 being connected to the second cooler 29. The product gas dried by the dryer is sent to a second gas compressor 44 for pressurization and then sent to a second cooler 29 for cooling.
Preferably, the fine separation unit further comprises a second heat exchange device 45, a heat medium inlet of the second heat exchange device 45 is connected with an outlet of the second gas compressor 44, and a heat medium outlet of the second heat exchange device 45 is connected with the second cooler 29; the cold medium inlet of the second heat exchange device 45 is connected with the liquid phase outlet of the first dealkylation tower 37, and the cold medium outlet of the second heat exchange device 45 is connected with the inlet of the hydrogenation device 38. The product gas pressurized by the compressor exchanges heat with the tower bottom liquid phase of the first dealkanization tower in the second heat exchange device, and then enters the second cooler for cooling, and the waste heat of the tower bottom liquid phase is fully utilized.
Preferably, the fine separation unit further includes a fifth cooler 46, a fifth gas-liquid separator 47, a gas phase outlet of the first de-alkane tower 37 is connected with the fifth cooler 46, the fifth cooler 46 is connected with the fifth gas-liquid separator 47, a liquid phase outlet of the fifth gas-liquid separator 47 is connected with a reflux inlet of the first de-alkane tower 37, and a gas phase outlet of the fifth gas-liquid separator 47 is connected with the synthesis gas separation unit. The gas phase at the top of the first dealkylation tower is cooled firstly, the liquid phase reflows after cooling, and the non-condensable gas is collected in the synthesis gas separation unit.
Preferably, the synthesis gas separation unit comprises a pressure swing adsorption device 48 and a hydrogen collection device, the gas phase outlet of the third gas-liquid separator 36 and the gas phase outlet of the first dealkylation tower 37 are connected with the inlet of the pressure swing adsorption device 48, the pressure swing adsorption device 48 is connected with the hydrogen collection device, and the hydrogen collection device is connected with the inlet of the hydrogenation device 38. The collected crude synthesis gas enters a pressure swing adsorption device, and hydrogen with certain purity is obtained after pressure swing adsorption separation and is stored in a hydrogen collection device.
The method for preparing olefin by reacting carbon dioxide with low-carbon alkane described in this embodiment is specifically a process method for preparing ethylene by reacting carbon dioxide with ethane, and specifically includes the following steps:
s1, introducing carbon dioxide and ethane into a feeding buffer tank according to a molar ratio of 1.4:1 to mix to obtain a raw material gas, introducing the raw material gas into a first waste heat exchange device to exchange heat with a product gas to carry out preliminary preheating, then introducing the raw material gas into a feeding preheating furnace, preheating to 100-300 ℃, then introducing the raw material gas into a feeding mixer to mix with 0.25Mpag of water vapor, reacting at the temperature of 911 ℃ and the pressure of 0.3MPa under the catalysis of an ethane dehydrogenation catalyst, wherein the ethane space velocity is 1300h-1Obtaining a product gas, wherein the product gas contains main products of carbon monoxide, hydrogen and ethylene, byproducts of methane, C3+ and the like and a small amount of unreacted raw materials of carbon dioxide, ethane and water;
s2, exchanging heat between the product gas and the raw material gas in a first waste heat exchange device, and primarily cooling the product gas by 300-500 ℃ by using waste heat in the product gas;
s2a, introducing the product gas obtained in the step S2 into a second waste heat exchange device for waste heat utilization, simultaneously further reducing the temperature of the product gas to 150-;
s3a, introducing gas obtained by gas-liquid separation into a first gas compressor to be compressed to the pressure of 4-5 Mpag;
s3, introducing the product gas compressed to a certain pressure into a decarburization absorption tower, and removing carbon dioxide in the product gas by using 20-40% of MDEA solution as an absorbent;
s3b, after the absorption of the absorbent is saturated, regenerating the MDEA rich solution in the decarburization absorption tower in a regeneration tower by using a gas stripping method, in the regeneration tower, firstly exchanging heat between the MDEA rich solution and the decarburized MDEA lean solution to 80-120 ℃, then enabling the MDEA rich solution to enter the regeneration tower, cooling the gas at the top of the regeneration tower to 40-80 ℃ through an air cooler, then cooling to 30-45 ℃ through a aftercooler, carrying out gas-liquid separation, refluxing the liquid obtained after the gas-liquid separation to the regeneration tower, and mixing the gas obtained after the gas-liquid separation with the carbon dioxide in the raw material gas for feeding;
s4, introducing the gas obtained in the step S3 into an alkaline washing tower, wherein MDEA is used as an absorbent in the alkaline washing tower, and removing trace carbon dioxide in the gas;
s5, introducing the gas obtained in the step S4 into a first cooler, cooling the gas to 15-20 ℃ by using a propylene refrigerant at the temperature of 10-15 ℃, and then introducing the gas into a first gas-liquid separator for gas-liquid separation;
s6, introducing the gas obtained by gas-liquid separation in the step S5 into a benzene washing tower to remove benzene therein;
s7, introducing the gas obtained in the step S6 into two dryers, wherein one dryer is operated, and the other dryer is regenerated;
s8a, introducing the dried gas into a second gas compressor, and compressing to a pressure of 3.5-4.5 MPag;
s8b, exchanging heat between the compressed gas and a tower bottom liquid phase product of a first dealkylation tower, and primarily cooling;
s8, introducing the product gas subjected to primary temperature reduction into a second cooler, cooling to 15-20 ℃ by using a propylene refrigerant at 10-15 ℃, introducing into a second gas-liquid separator for gas-liquid separation, conveying the separated gas into a third cooler for further cooling to-45 to-35 ℃, and introducing into a third gas-liquid separator for gas-liquid separation;
s9, introducing the liquid obtained by gas-liquid separation in the step S8 into a first dealkylation tower, wherein the first dealkylation tower is a demethanization rectifying tower, the working temperature is-35 to-21 ℃, the gas obtained by gas-liquid separation is sent to a synthesis gas separation unit, the gas-phase product at the top of the first dealkylation tower is condensed and refluxed by using a propylene refrigerant at the temperature of-40 ℃, and the uncondensed gas phase of the gas-phase product at the top of the tower is sent to the synthesis gas separation unit;
s10, sending the liquid phase product at the bottom of the tower subjected to demethanization in the step S9, which mainly contains ethylene, ethane, acetylene and the like, to a hydrogenation device for hydrogenation, and sending the gas phase product at the top of the first demethanizer to a synthesis gas separation unit;
s11, sending a product subjected to C2+ hydrotreating by a hydrogenation device to an olefin separation tower for separation, wherein the olefin separation tower is an ethylene separation and rectification tower, the working temperature is-40-50 ℃, a gas-phase product at the top of the olefin separation tower is condensed by using a refrigerant at the temperature of-50 to-40 ℃, the condensed liquid flows back, an uncondensed gas phase is sent to an olefin collection device, the olefin collection device is an ethylene collection device, and a liquid-phase product at the bottom of the tower is sent to a second dealkanization tower;
s12a, exchanging heat between a tower bottom liquid phase product of an olefin separation tower and a tower bottom liquid phase product of a second dealkylation tower, preliminarily preheating the tower bottom liquid phase product of the olefin separation tower, and fully utilizing the waste heat of the second dealkylation tower;
s12, introducing the liquid-phase product after preliminary preheating into a second dealkylation tower, wherein the second dealkylation tower is an ethane-removing rectifying tower, the working temperature is-30-60 ℃, condensing and refluxing a tower top gas-phase product of the second dealkylation tower, heating the non-condensable gas phase of the tower top gas-phase product to 10-15 ℃, mixing the non-condensable gas phase with ethane in raw material gas, feeding the mixture of the tower top gas-phase product passing through the second dealkylation tower and the ethane in the raw material gas in a mixed manner, cooling the tower bottom liquid-phase product to 40 ℃, cooling one path to 15 ℃ to be used as a washing liquid of a benzene washing tower, and using the other path as fuel of any device or devices in the system;
s13, conveying the gas sent to the synthesis gas separation unit to a pressure swing adsorption device at the temperature of 11-15 ℃ under the condition of 2-3MPag, separating hydrogen, storing the hydrogen in a hydrogen storage device, and then sending the desorbed gas out of the pressure swing adsorption device under the condition of 0.015-0.03 MPag.
EXAMPLE III
The process for preparing ethylene by reacting carbon dioxide and ethane in this example is the same as in example two except that in step S1, the molar ratio of carbon dioxide to ethane is 1.2:1, the reaction temperature is 700 ℃, and the ethane space velocity is 1300h-1。
Example four
Carbon dioxide in the examplesThe other parts of the process for preparing ethylene by reacting with ethane are the same as those in the second embodiment, except that in the second embodiment, in the step S1, the molar ratio of carbon dioxide to ethane is 1.0:1, the reaction temperature is 850 ℃, the reaction pressure is 0.45MPa, and the ethane space velocity is 1500h-1。
EXAMPLE five
The process for preparing ethylene by reacting carbon dioxide and ethane in this example is the same as in example two except that in step S1, the molar ratio of carbon dioxide to ethane is 0.6:1, the reaction temperature is 600 ℃, the reaction pressure is 0.4MPa, and the ethane space velocity is 2000h-1。
Table 1 is the product distribution that obtains in above-mentioned each embodiment, can derive by the result calculation, the utility model discloses a process for preparing ethylene by carbon dioxide and ethane reaction, ethylene and hydrogen average one-way total selectivity 60 ~ 85%, ethylene one-way selectivity is 65 ~ 85%, and the mole ratio of carbon monoxide and ethylene is 0.8 ~ 2.0 within a definite time, satisfies the proportion demand of enterprise's low reaches device to the raw materials just, still can adjust and control the product distribution through adjusting the raw materials proportion according to actual demand.
TABLE 1
EXAMPLE six
The method for preparing olefin by reacting carbon dioxide with light alkane described in this embodiment is specifically a process method for preparing propylene by reacting carbon dioxide with propane, and specifically includes the following steps:
s1, introducing carbon dioxide and propane into a feeding buffer tank according to a molar ratio of 1.4:1 to mix to obtain a raw material gas, introducing the raw material gas into a first waste heat exchange device to exchange heat with a product gas to carry out primary preheating, then introducing the raw material gas into a feeding preheating furnace, preheating to 100-300 ℃, then introducing the raw material gas into a feeding mixer to mix with 0.25Mpag of water vapor, reacting at the temperature of 731 ℃ and under the pressure of 0.3MPa under the catalysis of a propane dehydrogenation catalyst, wherein the propane space velocity is 2700h-1To obtain a product gas containing oneCarbon oxide, hydrogen, propylene main products, byproducts such as ethane and C4+ and a small amount of unreacted carbon dioxide, propane and water raw materials;
s2, exchanging heat between the product gas and the raw material gas in a first waste heat exchange device, and primarily cooling the product gas by 300-500 ℃ by using waste heat in the product gas;
s2a, introducing the product gas obtained in the step S2 into a second waste heat exchange device for waste heat utilization, simultaneously further reducing the temperature of the product gas to 150-;
s3a, introducing gas obtained by gas-liquid separation into a first gas compressor to be compressed to the pressure of 4-5 Mpag;
s3, introducing the product gas compressed to a certain pressure into a decarburization absorption tower, and removing carbon dioxide in the product gas by using 20-40% of MDEA solution as an absorbent;
s3b, after the absorption of the absorbent is saturated, regenerating the MDEA rich solution in the decarburization absorption tower in a regeneration tower by using a gas stripping method, in the regeneration tower, firstly exchanging heat between the MDEA rich solution and the decarburized MDEA lean solution to 80-120 ℃, then enabling the MDEA rich solution to enter the regeneration tower, cooling the gas at the top of the regeneration tower to 40-80 ℃ through an air cooler, then cooling to 30-45 ℃ through a aftercooler, carrying out gas-liquid separation, refluxing the liquid obtained after the gas-liquid separation to the regeneration tower, and mixing the gas obtained after the gas-liquid separation with the carbon dioxide in the raw material gas for feeding;
s4, introducing the gas obtained in the step S3 into an alkaline washing tower, wherein the alkaline washing tower takes MDEA as an absorbent to remove trace carbon dioxide in the gas;
s5, introducing the gas obtained in the step S4 into a first cooler, cooling the gas to 15-20 ℃ by using a propylene refrigerant at the temperature of 10-15 ℃, and then introducing the gas into a first gas-liquid separator for gas-liquid separation;
s6, introducing the gas obtained by gas-liquid separation in the step S5 into a benzene washing tower to remove benzene therein;
s7, introducing the gas obtained in the step S6 into two dryers, wherein one dryer is operated, and the other dryer is regenerated;
s8a, introducing the dried gas into a second gas compressor, and compressing to a pressure of 3.5-4.5 MPag;
s8b, exchanging heat between the compressed gas and a tower bottom liquid phase product of a first dealkylation tower, and primarily cooling;
s8, introducing the product gas subjected to primary temperature reduction into a second cooler, cooling to 15-20 ℃ by using a propylene refrigerant at 10-15 ℃, introducing into a second gas-liquid separator for gas-liquid separation, conveying the separated gas into a third cooler for further cooling to-45 to-35 ℃, and introducing into a third gas-liquid separator for gas-liquid separation;
s9, introducing the liquid obtained by gas-liquid separation in the step S8 into a first dealkylation tower, wherein the first dealkylation tower is an deethanization rectifying tower, the working temperature is-35 to-21 ℃, the gas obtained by gas-liquid separation is sent to a synthesis gas separation unit, the gas-phase product at the top of the first dealkylation tower is condensed and refluxed by using a propylene refrigerant at-40 ℃, and the uncondensed gas phase of the gas-phase product at the top of the first dealkylation tower is sent to the synthesis gas separation unit;
s10, sending the liquid phase product at the bottom of the first dealkylation tower, which is subjected to deethanization in the step S9 and mainly contains propylene, propane, propyne and the like, to a hydrogenation device for hydrogenation, and sending the gas phase product at the top of the first dealkylation tower to a synthesis gas separation unit;
s11, sending a product subjected to C3+ hydrotreating by a hydrogenation device to an olefin separation tower for separation, wherein the olefin separation tower is a propylene separation and rectification tower, the working temperature is-40-50 ℃, a gas-phase product at the top of the olefin separation tower is condensed by using a refrigerant at the temperature of-50 to-40 ℃, the condensed liquid reflows, an uncondensed gas phase is sent to an olefin collection device, the olefin collection device is a propylene collection device, and a liquid-phase product at the bottom of the tower is sent to a second dealkylation tower;
s12a, exchanging heat between a tower bottom liquid phase product of an olefin separation tower and a tower bottom liquid phase product of a second dealkylation tower, preliminarily preheating the tower bottom liquid phase product of the olefin separation tower, and fully utilizing the waste heat of the second dealkylation tower;
s12, introducing the liquid-phase product after preliminary preheating into a second dealkylation tower, wherein the second dealkylation tower is a depropanization rectifying tower, the working temperature is-30-60 ℃, condensing and refluxing a top gas-phase product of the second dealkylation tower, heating the non-condensable gas phase of the top gas-phase product to 10-15 ℃, mixing the non-condensable gas phase with propane in the raw material gas, feeding the top gas-phase product of the second dealkylation tower and the propane in the raw material gas in a mixed manner, cooling the bottom liquid-phase product to 40 ℃ to obtain a C4+, cooling one path to 15 ℃ as a washing liquid of a benzene washing tower, and using the other path as a fuel of any device or devices in the system;
s13, conveying the gas sent to the synthesis gas separation unit to a pressure swing adsorption device at the temperature of 11-15 ℃ under the condition of 2-3MPag, separating hydrogen, storing the hydrogen in a hydrogen storage device, and then sending the desorbed gas out of the pressure swing adsorption device under the condition of 0.015-0.03 MPag.
Table 2 shows the distribution of the products obtained in the sixth example, and it can be found from the results that the process for producing propylene by the reaction of carbon dioxide and propane according to the present invention has an average once-through total selectivity of propylene and hydrogen of 72% to 85% (by mass), a once-through selectivity of propylene of 65% to 70% (by mass), and a molar ratio of carbon monoxide to propylene of 0.3 to 0.6.
TABLE 2
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications can be made without departing from the scope of the invention.
Claims (10)
1. A device for preparing olefin by reacting carbon dioxide with low-carbon alkane is characterized in that: the device comprises a feed inlet, a feed preheating furnace and a reaction furnace, wherein the feed inlet is connected with an inlet of the feed preheating furnace, an outlet of the feed preheating furnace is connected with an inlet of the reaction furnace, and an inlet of the reaction furnace is provided with a first gas distributor; the reaction furnace comprises a reaction furnace shell, wherein a plurality of layers of heating areas are arranged in the reaction furnace shell, and the heating areas are surrounded by a first heating wall; a plurality of rows of reaction tubes are arranged in each layer of heating area in parallel, one end of each reaction tube is connected with the first gas distributor, and the other end of each reaction tube is connected with an outlet of the reaction furnace; a plurality of first heating nozzles are arranged between the reaction tubes.
2. The apparatus of claim 1, wherein the carbon dioxide is reacted with a light alkane to produce an olefin, the apparatus comprising: the waste heat recovery device comprises a first waste heat exchange device and a second waste heat exchange device, wherein the first waste heat exchange device comprises a tube side and a shell side; an outlet of the reaction furnace is connected with a tube pass inlet of the first waste heat exchange device, and a tube pass outlet of the first waste heat exchange device is connected with a discharge hole; the feeding hole is connected with a shell pass inlet of the first waste heat exchange device, and a shell pass outlet of the first waste heat exchange device is connected with an inlet of the feeding preheating furnace.
3. The apparatus of claim 1, wherein the carbon dioxide is reacted with a light alkane to produce an olefin, the apparatus comprising: the feed preheating furnace comprises a preheating furnace shell; a second heating wall is arranged on the inner wall of the preheating furnace shell; a second gas distributor is arranged at the inlet of the feeding preheating furnace; a plurality of rows of preheating pipes are arranged in the preheating furnace shell in parallel, one end of each preheating pipe is connected with the second gas distributor, and the other end of each preheating pipe is connected with an outlet of the feeding preheating furnace; and a plurality of second heating nozzles are arranged between the preheating pipes.
4. The apparatus of claim 1, wherein the carbon dioxide is reacted with a light alkane to produce an olefin, the apparatus comprising: the feeding device is characterized by also comprising a feeding mixer suitable for mixing carbon dioxide, low-carbon alkane and steam, wherein the feeding mixer is provided with a steam inlet, the inlet of the feeding mixer is connected with the outlet of the feeding preheating furnace, and the outlet of the feeding mixer is connected with the inlet of the reaction furnace.
5. A system for preparing olefin by reacting carbon dioxide with low-carbon alkane is characterized in that: the device for preparing the olefin by the reaction of the carbon dioxide and the light alkane according to any one of claims 1 to 4, further comprising a first waste heat exchange device, a second waste heat exchange device and a quenching device; the hot medium inlet of the first waste heat exchange device is connected with the outlet of the reaction furnace, the hot medium outlet of the first waste heat exchange device is connected with the hot medium inlet of the second waste heat exchange device, the cold medium inlet of the first waste heat exchange device is connected with the feed inlet, and the cold medium outlet of the first waste heat exchange device is connected with the inlet of the feed preheating furnace; and a heat medium outlet of the second waste heat exchange device is connected with a heat medium inlet of the quenching device, and a heat medium outlet of the quenching device is connected with a discharge hole.
6. The system for producing olefin hydrocarbon by the reaction of carbon dioxide and light alkane according to claim 5, wherein: the system also comprises a coarse separation unit, wherein the coarse separation unit comprises a decarburization absorption tower, an alkaline washing tower, a first cooler, a first gas-liquid separator, a regeneration tower, a benzene washing tower and a dryer; a hot medium outlet of the quenching device is connected with a gas phase inlet of the decarburization absorption tower, a gas phase outlet of the decarburization absorption tower is connected with a gas phase inlet of the alkaline washing tower, a gas phase outlet of the alkaline washing tower is connected with the first cooler, the first cooler is connected with the first gas-liquid separator, a gas phase outlet of the first gas-liquid separator is connected with a gas phase inlet of the benzene washing tower, a gas phase outlet of the benzene washing tower is connected with an inlet of the dryer, and an outlet of the dryer is connected with the discharge hole; and a liquid phase outlet of the decarburization absorption tower is connected with a liquid phase inlet of the regeneration tower, a gas phase outlet of the regeneration tower is connected with the feed inlet, and a liquid phase outlet of the regeneration tower is connected with a liquid phase inlet of the decarburization absorption tower.
7. The system for producing olefin hydrocarbon by the reaction of carbon dioxide and light alkane according to claim 6, wherein: the rough separation unit further comprises a first heat exchange device, a heat medium inlet of the first heat exchange device is connected with a liquid phase outlet of the regeneration tower, a heat medium outlet of the first heat exchange device is connected with a liquid phase inlet of the decarburization absorption tower, a cold medium inlet of the first heat exchange device is connected with a liquid phase outlet of the decarburization absorption tower, and a cold medium outlet of the first heat exchange device is connected with a liquid phase inlet of the regeneration tower.
8. The system for producing olefin by reacting carbon dioxide with light alkane according to claim 6 or 7, wherein: the system also comprises a fine separation unit, wherein the fine separation unit comprises a second cooler, a second gas-liquid separator, a third cooler, a third gas-liquid separator, a first dealkylation tower, a hydrogenation device, an olefin separation tower, an olefin collection device and a second dealkylation tower; an outlet of the dryer is connected with the second cooler, the second cooler is connected with the second gas-liquid separator, a gas-phase outlet of the second gas-liquid separator is connected with the third cooler, the third cooler is connected with the third gas-liquid separator, a liquid-phase outlet of the third gas-liquid separator is connected with a liquid-phase inlet of the first dealkylation tower, a gas-phase outlet of the third gas-liquid separator is connected with a synthesis gas separation unit, a gas-phase outlet of the first dealkylation tower is connected with the synthesis gas separation unit, a liquid-phase outlet of the first dealkylation tower is connected with an inlet of the hydrogenation device, an outlet of the hydrogenation device is connected with a liquid-phase inlet of the olefin separation tower, a gas-phase outlet of the olefin separation tower is connected with the olefin collection device, and a liquid-phase outlet of the olefin separation tower is connected with a liquid-phase inlet of the second dealkylation tower, and a gas phase outlet of the second dealkylation tower is connected with the feed inlet, and a liquid phase outlet of the second dealkylation tower is connected with a liquid phase inlet of the benzene washing tower.
9. The system for producing olefin hydrocarbon by the reaction of carbon dioxide and light alkane according to claim 8, wherein: the fine separation unit also comprises a second heat exchange device, a heat medium inlet of the second heat exchange device is connected with an outlet of the dryer, and a heat medium outlet of the second heat exchange device is connected with the second cooler; and a cold medium inlet of the second heat exchange device is connected with a liquid phase outlet of the first dealkylation tower, and a cold medium outlet of the second heat exchange device is connected with an inlet of the hydrogenation device.
10. The system for producing olefin hydrocarbon by the reaction of carbon dioxide and light alkane according to claim 8, wherein: the synthesis gas separation unit comprises a pressure swing adsorption device and a hydrogen collection device, a gas phase outlet of the third gas-liquid separator and a gas phase outlet of the first dealkylation tower are connected with an inlet of the pressure swing adsorption device, the pressure swing adsorption device is connected with the hydrogen collection device, and the hydrogen collection device is connected with an inlet of the hydrogenation device.
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