Carbon dioxide integrated deep purification system

Abstract

The present application relates to greenhouse gas emission reduction technical field, especially a kind of carbon dioxide integrated deep purification system.The technical scheme used in the present application is: including first carbon dioxide fine desulfurization reactor, second carbon dioxide fine desulfurization reactor and high-temperature carbon dioxide cooler, the tower bottom gas phase outlet pipeline of first carbon dioxide fine desulfurization reactor and second carbon dioxide fine desulfurization reactor is connected with the high-temperature carbon dioxide cooler, the gas phase outlet pipeline of first carbon dioxide fine desulfurization reactor is connected with the gas phase inlet pipe of second carbon dioxide fine desulfurization reactor, the gas phase outlet pipeline of second carbon dioxide fine desulfurization reactor is connected with the gas phase inlet pipe of the first carbon dioxide fine desulfurization reactor.The present application has the advantages of: high purification degree, catalyst recovery is easy, desulfurization comprehensive cost is low, overall operation process is more stable, the performance-price ratio is higher when using, control precision is higher, the security in running process is more reliable.

Description

TECHNICAL FIELD

[0001] The application relates to a greenhouse gas emission reduction technology field, in particular to a carbon dioxide integrated deep purification system. BACKGROUND

[0002] With the rapid development of human industry and the increasing demand for energy, the amount of carbon dioxide in industrial emissions is also increasing. Large amounts of carbon dioxide emissions will cause the greenhouse effect of the atmosphere, exacerbate global warming and climate change. Therefore, reducing carbon dioxide emissions has become an urgent task.

[0003] The chemical industry is constantly innovating various carbon recycling process routes with great prospects. With the rapid development of the chemical industry, carbon dioxide has been widely used in the chemical industry. At the same time, the demand for high-purity carbon dioxide has also increased dramatically. At present, the highest standard for carbon dioxide products is GB 1886.228-2016 "National Food Safety Standard / Food Additives / Carbon Dioxide". The standard stipulates that the food-grade CO2 has "3 sensory requirements, 18 physicochemical indicators", a total of 21 indicators (after conversion, the CO2 purity is required to be greater than or equal to 99.9%), and the total sulfur (except SO2) content is required to be less than or equal to 0.1 muL / L. Then with the continuous updating of technology, many process routes in the chemical industry require CO2 much higher than the existing standard, especially the total sulfur (except SO2) content requirement needs to reach less than or equal to 0.03 muL / L.

[0004] Therefore, the industry urgently needs to develop a carbon dioxide integrated deep purification system suitable for large-scale industrial production of the chemical industry under high-temperature complex atmosphere. SUMMARY

[0005] The purpose of the present application is to provide a carbon dioxide integrated deep purification system, which can realize the deep purification of industrial carbon dioxide gas, and the high-purity carbon dioxide obtained can be used as a carbon resource. At the same time of realizing CO2 emission reduction, it can replace the large consumption of fossil energy such as coal in traditional chemical industry, guarantee energy security, reduce water resource consumption and pollution emission, and also create more economic benefits. The deep purification system uses Zn / Cu type catalyst to hydrogenate trace organic sulfur in high-temperature complex atmosphere carbon dioxide gas into H2S, and the catalyst adsorbs H2S on the surface of the catalyst. Then ZnO reacts with H2S to perform chemical purification. The purification degree is high, the catalyst is easy to recover, the desulfurization comprehensive cost is low, the overall operation process is more stable, the cost performance is higher during use, the control precision is higher, and the safety during operation is more reliable.

[0006] The technical scheme of the present application is as follows:

[0007] The application discloses a carbon dioxide integrated deep purification system, which is characterized by comprising a first carbon dioxide fine desulfurization reactor, a second carbon dioxide fine desulfurization reactor and a high-temperature carbon dioxide cooler, wherein a gas phase outlet pipeline at the bottom of the first carbon dioxide fine desulfurization reactor and the second carbon dioxide fine desulfurization reactor is connected with the high-temperature carbon dioxide cooler, a gas phase outlet pipeline of the first carbon dioxide fine desulfurization reactor is connected with a gas phase inlet pipeline of the second carbon dioxide fine desulfurization reactor, a gas phase outlet pipeline of the second carbon dioxide fine desulfurization reactor is connected with a gas phase inlet pipeline of the first carbon dioxide fine desulfurization reactor, the first carbon dioxide fine desulfurization reactor and the second carbon dioxide fine desulfurization reactor are completely identical in specification, a middle position of the first carbon dioxide fine desulfurization reactor is a cylindrical middle purification reaction zone, and end portions of the first carbon dioxide fine desulfurization reactor are carbon dioxide raw material gas inlets; one side of the middle purification reaction zone close to the carbon dioxide raw material gas inlets is provided with a first alumina porcelain ball layer, a pressure grid, an upper buffer zone and an oval upper end cover; the other side of the middle purification reaction zone is provided with a second alumina porcelain ball layer, a filler support grid, an oval lower end cover and a skirt; a connection position of the second alumina porcelain ball layer and the filler support grid is provided with a filler discharge port; a right side of the filler support grid is provided with a carbon dioxide purified gas outlet and a lower inlet hole at a connection position of the filler support grid and the oval lower end cover; and the skirt is provided with a skirt inspection hole and a bottom blowdown port.

[0008] Further, the first carbon dioxide fine desulfurization reactor and the second carbon dioxide fine desulfurization reactor are fixed bed reactors, and a mean value and mean amount gas distributor is arranged at a position of the upper buffer zone and a connection position of the carbon dioxide raw material gas inlets.

[0009] Further, Zn / Cu type catalysts are filled in catalyst bed layers of the first carbon dioxide fine desulfurization reactor and the second carbon dioxide fine desulfurization reactor.

[0010] Further, the Zn / Cu type catalysts can generate stable compounds with H2S, COS, RSH and the like, so that sulfur can be removed to below 0.03 ppm.

[0011] Further, the high-temperature carbon dioxide cooler is a shell-and-tube heat exchanger, the cooling liquid in the high-temperature carbon dioxide cooler is cooling water, and carbon dioxide gas passes through the shell side of the shell-and-tube heat exchanger, and the cooling water passes through the tube side of the shell-and-tube heat exchanger.

[0012] Further, the integral mounting support base is detachably connected with the cylinder structure, reinforcing support ribs are arranged on the integral mounting support base, fastening connection support corners are arranged on the side surface of the integral mounting support base, and fastening mounting flanges are arranged on the lower end of the integral mounting support base.

[0013] Further, sealing combined safety columns are arranged on the outer end portions of the circulating cooling water inlet, the high-purity carbon dioxide gas outlet, the high-purity carbon dioxide gas inlet and the circulating cooling water outlet.

[0014] The present application has the following beneficial effects:

[0015] 1. The present application can realize deep purification of industrial carbon dioxide gas, and the obtained high-purity carbon dioxide can be used as a carbon resource, which can realize CO2 emission reduction, replace the large consumption of fossil energy such as coal in traditional chemical industry, guarantee energy security, reduce water consumption and pollution emission, and create more economic benefits.

[0016] 2. The deep purification system utilizes Zn / Cu type catalyst to hydrogenate trace organic sulfur in high-temperature complex atmosphere carbon dioxide gas into H2S, and the catalyst adsorbs H2S on the surface of the catalyst, then ZnO reacts with H2S to perform chemical purification, which has high purification degree, easy catalyst recovery, low desulfurization comprehensive cost, more stable overall operation process, higher cost performance in use, higher control precision, and more reliable safety in operation process. BRIEF DESCRIPTION OF DRAWINGS

[0017] Fig. 1 It is a system connection schematic diagram of the present application;

[0018] Fig. 2 It is a structure schematic diagram of the first carbon dioxide fine desulfurization reactor of the present application;

[0019] Fig. 3 It is a structure schematic diagram of the high-temperature carbon dioxide cooler of the present application;

[0020] In the figure: 1, the first carbon dioxide fine desulfurization reactor, 2, the second carbon dioxide fine desulfurization reactor, 3, high-temperature carbon dioxide cooler, 11, carbon dioxide raw gas inlet, 12, average amount of gas distributor, 13, oval upper head, 14, upper buffer zone, 15, upper inlet hole, 16, pressure grid, 17, the first alumina porcelain ball layer, 18, plain wire mesh, 19, middle purification reaction zone, 31, oval cooler head, 32, cylinder structure, 33, circulating cooling water inlet, 34, high-purity carbon dioxide gas outlet, 35, heat exchange tube installation stabilizing plate, 36, integral installation support seat, 37, front baffle, 38, rear baffle, 39, heat exchange tube, 110, filler discharge port, 111, the second alumina porcelain ball layer, 112, filler support grid, 113, carbon dioxide purification gas outlet, 114, lower inlet hole, 115, oval lower head, 116, bottom blowdown, 117, apron inspection hole, 118, apron, 310, high-purity carbon dioxide gas inlet, 311, circulating cooling water outlet. DETAILED DESCRIPTION

[0021] As Figs. 1 to 3The illustrated carbon dioxide integrated deep purification system includes a first carbon dioxide fine desulfurization reactor 1, a second carbon dioxide fine desulfurization reactor 2 and a high-temperature carbon dioxide cooler 3. The bottom gas phase outlet pipeline of the first carbon dioxide fine desulfurization reactor 1 and the second carbon dioxide fine desulfurization reactor 2 is connected with the high-temperature carbon dioxide cooler 3. The gas phase outlet pipeline of the first carbon dioxide fine desulfurization reactor 1 is connected with the gas phase inlet pipeline of the second carbon dioxide fine desulfurization reactor 2. The gas phase outlet pipeline of the second carbon dioxide fine desulfurization reactor 2 is connected with the gas phase inlet pipeline of the first carbon dioxide fine desulfurization reactor 1. The first carbon dioxide fine desulfurization reactor 1 and the second carbon dioxide fine desulfurization reactor 2 are completely identical in specification. The middle position of the first carbon dioxide fine desulfurization reactor 1 is a cylindrical middle purification reaction zone 19. The end of the first carbon dioxide fine desulfurization reactor 1 is a carbon dioxide raw material gas inlet 11. The side close to the carbon dioxide raw material gas inlet 11 of the middle purification reaction zone 19 is provided with a first alumina porcelain ball layer 17, a plain wire mesh 18, a pressure grid 16, an upper buffer zone 14 and an oval upper head 13. The position of the upper buffer zone 14 is provided with an upper inlet hole 15. The other side of the middle purification reaction zone 19 is provided with a second alumina porcelain ball layer 111, a filler support grid 112, an oval lower head 115 and a skirt 118. The connection position of the second alumina porcelain ball layer 111 and the filler support grid 112 is provided with a filler discharge port 110. The right side of the filler support grid 112 is provided with a carbon dioxide purified gas outlet 113 and a lower inlet hole 114 at the connection position with the oval lower head 115. The skirt 118 is provided with a skirt inspection hole 117 and a bottom blowdown port 116. The main body of the high-temperature carbon dioxide cooler 3 is a cylindrical cylinder structure 32. The two ends of the cylinder structure 32 are provided with oval cooler heads 31. The lower part of the cylinder structure 32 is provided with an integral mounting support seat 36. The inside of the cylinder structure 32 is provided with heat exchange pipes 39 uniformly distributed in the circumference. The heat exchange pipes 39 are connected and combined together through front baffle plates 37 and rear baffle plates 38 distributed on the left and right. The left and right sides of the heat exchange pipes 39 are respectively provided with heat exchange pipe mounting stabilizing plates 35. The left and right sides of the cylinder structure 32 are respectively provided with a circulating cooling water inlet 33 and a circulating cooling water outlet 311. The position close to the circulating cooling water inlet 33 of the cylinder structure 32 is provided with a high-purity carbon dioxide gas outlet 34. The position close to the circulating cooling water outlet 311 of the cylinder structure 32 is provided with a high-purity carbon dioxide gas inlet 310.It can realize the deep purification of industrial carbon dioxide gas, and the high-purity carbon dioxide obtained can be used as a carbon resource. While achieving CO2 emission reduction, it can replace the large consumption of fossil energy such as coal in traditional chemical industry, ensure energy security, reduce water consumption and pollution emissions, and create more economic benefits. The deep purification system uses Zn / Cu type catalyst to hydrogenate trace organic sulfur in high-temperature complex atmosphere carbon dioxide gas into H2S, and the catalyst adsorbs H2S on the surface of the catalyst, and then ZnO reacts with H2S to perform chemical purification. The purification degree is high, the catalyst is easy to recover, the desulfurization comprehensive cost is low, the overall operation process is more stable, the cost performance is higher during use, the control precision is higher, and the safety during operation is more reliable.

[0022] The first and second carbon dioxide desulfurization reactors have a carbon dioxide raw material gas feed port at the top of the tower, and a carbon dioxide purified gas outlet at the bottom. A homogeneous and uniform gas distributor is provided at the carbon dioxide raw material gas feed port at the top of the tower, and the alumina ceramic ball layer is arranged in two layers, with ceramic ball specifications of φ6mm corundum ceramic ball and φ13mm corundum ceramic ball. The middle purification reaction zone uses ZnO / CuO material type catalyst filler, with specifications of gray strip-shaped objects with a diameter of 3-5mm and a density range of 0.85kg / L-1.1kg / L.

[0023] The high-temperature carbon dioxide cooler 3 is in the form of a shell-and-tube heat exchanger, with the tube inlet connected to the circulating cooling water supply line CWS and the tube outlet connected to the circulating cooling water return line CWR. The shell inlet is connected to the outlet pipeline of the upstream carbon dioxide desulfurization reactor, and the shell outlet is connected to the inlet pipeline of the downstream section. The heat exchange tubes are arranged in a 30° equilateral triangle.

[0024] The process flow of the system is as follows:

[0025] The carbon dioxide raw gas (composition: CO2 97.3981 mol%, N2: 0.431 mol%, H2: 0.0034 mol%, CO: 0.0068 mol%, CH3OH: 0.0023 mol%, H2S: 0.00011375 mol%, COS: 0.00002839 mol%, H2O: 2.1582 mol%, Ar: 0.00000829 mol%, CH4: 0.00001136 mol%) of the upstream section enters the carbon dioxide desulfurization reactor 1 through the pipeline, enters the reactor after entering the carbon dioxide raw gas inlet of the carbon dioxide desulfurization reactor 1 tower, and enters the catalyst bed in a uniform distribution manner after passing through the average amount gas distributor to carry out the purification reaction (at this time, the hot spot temperature of the catalyst bed is 160°C, the reaction pressure is 2.6 MPaG, and the space velocity is 373 h-1). During normal operation, the two carbon dioxide desulfurization reactors are operated in series, and the purified carbon dioxide raw gas after passing through the first carbon dioxide desulfurization reactor 1 enters the second carbon dioxide desulfurization reactor 2 through the pipeline, and enters the catalyst bed in a uniform distribution manner after passing through the average amount gas distributor to carry out the purification reaction (at this time, the hot spot temperature of the catalyst bed is 160°C, the reaction pressure is 2.6 MPaG, and the space velocity is 373 h-1).

[0026] The carbon dioxide purification gas product (composition: CO2 97.3981 mol%, N2: 0.431 mol%, H2: 0.0034 mol%, CO: 0.0068 mol%, CH3OH: 0.0023 mol%, H2S+COS: ≤30ppb, H2O: 2.1583 mol%, Ar: 0.000008 mol%, CH4: 0.000011 mol%) after purification enters the high-temperature carbon dioxide cooler 3 (inner diameter DN1200mm, heat exchange pipe straight section length 4500mm, heat exchange area: 275.7㎡) and is cooled to 43°C after heat exchange cooling with circulating cooling water (33°C), and is sent out to the downstream section inlet pipeline.

[0027] In summary, the carbon dioxide integrated purification system can realize continuous operation of the purification process, the first carbon dioxide desulfurization reactor and the second carbon dioxide desulfurization reactor are operated in series during normal operation, the packing can be cut out when replacing, which does not affect the normal operation of the purification process, the energy consumption is exchanged with simple and reasonable configuration, the operation difficulty is reduced, and the investment cost is reduced. In addition, the circulating pipeline is arranged on the outlet pipeline of the high-temperature carbon dioxide cooler 3, is connected with the circulating cooling water inlet pipeline of the high-temperature carbon dioxide cooler 3, can greatly reduce the use amount of the cooling water, and reduces the production energy consumption.

[0028] As preferred, the first carbon dioxide fine desulfurization reactor 1 and the second carbon dioxide fine desulfurization reactor 2 are both fixed bed reactors, and a mean amount gas distributor 12 is arranged at the position where the upper buffer zone 14 is connected with the carbon dioxide raw material gas inlet 11, so as to ensure higher control accuracy and higher safety of the gas delivery.

[0029] As preferred, the catalyst bed of the first carbon dioxide fine desulfurization reactor 1 and the second carbon dioxide fine desulfurization reactor 2 is filled with Zn / Cu type catalyst.

[0030] As preferred, the Zn / Cu type catalyst can generate stable compounds with H2S, COS, RSH and other substances, so as to remove sulfur to below 0.03 ppm, and meanwhile, the catalyst has dechlorination effect, so as to ensure higher reaction efficiency.

[0031] As preferred, the high-temperature carbon dioxide cooler 3 is a tube-shell heat exchanger, and the cooling liquid in the high-temperature carbon dioxide cooler 3 is cooling water, and the carbon dioxide gas passes through the shell side of the tube-shell heat exchanger, and the cooling water passes through the tube side of the tube-shell heat exchanger, so as to have lower cost in use.

[0032] As preferred, the integral mounting support seat 36 is detachably connected with the cylinder structure 32, and reinforcing support ribs are arranged on the integral mounting support seat 36, fastening connection branches are arranged on the side surface of the integral mounting support seat 36, and fastening mounting flanges are arranged on the lower end of the integral mounting support seat 36, so as to have better fastening when mounting and fixing, and the mounting operation is easier.

[0033] As preferred, sealing combination safety columns are arranged on the outer end portions of the circulating cooling water inlet 33, the high-purity carbon dioxide gas outlet 34, the high-purity carbon dioxide gas inlet 310 and the circulating cooling water outlet 311, so as to have better sealing at the connection position, higher compression strength at the connection position, and stronger durability in use.

[0034] The above is the preferred embodiment of the present application, and it should be noted that those skilled in the art can make some improvements or replacements without departing from the principles of the present application, and these improvements or replacements should also be considered as the protection scope of the present application.

Claims

1. A carbon dioxide integrated deep purification system, characterized in that: The application relates to a high-temperature carbon dioxide cooling device, which comprises a first carbon dioxide fine desulfurization reactor (1), a second carbon dioxide fine desulfurization reactor (2) and a high-temperature carbon dioxide cooler (3), the tower bottom gas phase outlet pipelines of the first carbon dioxide fine desulfurization reactor (1) and the second carbon dioxide fine desulfurization reactor (2) are connected with the high-temperature carbon dioxide cooler (3), the gas phase outlet pipeline of the first carbon dioxide fine desulfurization reactor (1) is connected with the gas phase inlet pipeline of the second carbon dioxide fine desulfurization reactor (2), the gas phase outlet pipeline of the second carbon dioxide fine desulfurization reactor (2) is connected with the gas phase inlet pipeline of the first carbon dioxide fine desulfurization reactor (1), the first carbon dioxide fine desulfurization reactor (1) and the second carbon dioxide fine desulfurization reactor (2) are completely identical in specification, the middle position of the first carbon dioxide fine desulfurization reactor (1) is a cylindrical middle purification reaction zone (19), the end of the first carbon dioxide fine desulfurization reactor (1) is a carbon dioxide raw material gas inlet (11), one side of the middle purification reaction zone (19) close to the carbon dioxide raw material gas inlet (11) is provided with a first alumina porcelain ball layer (17), a plain wire mesh (18), a pressure grid (16), an upper buffer zone (14) and an oval upper end cover (13), the position of the upper buffer zone (14) is provided with an upper inlet hole (15), the other side of the middle purification reaction zone (19) is provided with a second alumina porcelain ball layer (111), a filler support grid (112), an oval lower end cover (115) and a skirt (118), the connecting position of the second alumina porcelain ball layer (111) and the filler support grid (112) is provided with a filler discharge port (110), the right side of the filler support grid (112) is provided with a carbon dioxide purified gas outlet (113) and a lower inlet hole (114) at the connecting position of the oval lower end cover (115), the skirt (118) is provided with a skirt inspection hole (117) and a bottom blowdown port (116); the main body of the high-temperature carbon dioxide cooler (3) is a cylindrical cylinder structure (32), the two ends of the cylinder structure (32) are provided with oval cooler end covers (31), the lower portion of the cylinder structure (32) is provided with an integral mounting support base (36), the inside of the cylinder structure (32) is provided with heat exchange pipes (39) which are uniformly distributed in a circle, the heat exchange pipes (39) are connected and combined together through left and right distributed front baffle plates (37) and rear baffle plates (38), the left and right sides of the heat exchange pipes (39) are respectively provided with heat exchange pipe mounting stabilizing plates (35), the left and right sides of the cylinder structure (32) are respectively provided with a circulating cooling water inlet (33) and a circulating cooling water outlet (311), the position of the cylinder structure (32) close to the circulating cooling water inlet (33) is provided with a high-purity carbon dioxide gas outlet (34), the position of the cylinder structure (32) close to the circulating cooling water outlet (311) is provided with a high-purity carbon dioxide gas inlet (310).

2. The integrated carbon dioxide deep purification system according to claim 1, wherein: The first carbon dioxide fine desulfurization reactor (1) and the second carbon dioxide fine desulfurization reactor (2) are fixed bed reactors, and a mean amount gas distributor (12) is arranged at the position where the upper buffer zone (14) is connected with the carbon dioxide raw material gas inlet (11).

3. The integrated carbon dioxide deep purification system of claim 1, wherein: The catalyst bed of the first carbon dioxide fine desulfurization reactor (1) and the second carbon dioxide fine desulfurization reactor (2) is filled with Zn / Cu type catalyst.

4. The integrated carbon dioxide deep purification system of claim 3, wherein: The Zn / Cu type catalyst can generate stable compounds with H2S, COS and RSH to remove sulfur to below 0.03 ppm.

5. The integrated carbon dioxide deep purification system of claim 1, wherein: The high-temperature carbon dioxide cooler (3) is a tube-shell heat exchanger, the cooling liquid in the high-temperature carbon dioxide cooler (3) is cooling water, and carbon dioxide gas passes through the shell side of the tube-shell heat exchanger, and the cooling water passes through the tube side of the tube-shell heat exchanger.

6. The integrated carbon dioxide deep purification system of claim 1, wherein: The integral mounting support seat (36) is detachably connected with the cylinder structure (32), the integral mounting support seat (36) is provided with reinforcing support ribs, the side surface of the integral mounting support seat (36) is provided with a fastening connection support corner, and the lower end of the integral mounting support seat (36) is provided with a fastening mounting flange.

7. The integrated carbon dioxide deep purification system of claim 1, wherein: The outer end of the circulating cooling water inlet (33), the high-purity carbon dioxide gas outlet (34), the high-purity carbon dioxide gas inlet (310) and the circulating cooling water outlet (311) are all provided with sealing combined safety columns.

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