CN210885949U - System for preparing LNG (liquefied Natural gas) by sulfur-resistant uniform-temperature methanation of medium-low-temperature dry distillation raw gas - Google Patents
System for preparing LNG (liquefied Natural gas) by sulfur-resistant uniform-temperature methanation of medium-low-temperature dry distillation raw gas Download PDFInfo
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- CN210885949U CN210885949U CN201921835004.6U CN201921835004U CN210885949U CN 210885949 U CN210885949 U CN 210885949U CN 201921835004 U CN201921835004 U CN 201921835004U CN 210885949 U CN210885949 U CN 210885949U
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Abstract
The utility model discloses a system for well low temperature dry distillation raw coke oven gas is through resistant sulphur samming methanation system LNG belongs to the clean high-efficient technical field that utilizes of coal. Performing dust removal, deamination and purification on the dry distillation raw gas, and then recovering tar to obtain a high-value byproduct; then the high-grade hydrocarbons such as propane and butane are directly prepared into LPG by pressurization, liquefaction and separation. H desorbed from desulfurization and decarbonization device2The S gas has high purity, and sulfur can be recovered by adopting a Claus sulfur recovery process. LNG component CH obtained after cryogenic liquefaction separation4The content is high and is more than 95 percent, and the requirement of a first-grade natural gas product is met. The system is simple and convenient to operate, realizes clean and efficient utilization of low-rank coal by adopting a low-temperature destructive distillation poly-generation technology of the coal, produces liquefied natural gas with high calorific value and byproducts such as tar, LPG, sulfur, carbon dioxide and the like, saves energy and has high economic benefit.
Description
Technical Field
The utility model belongs to the technical field of the clean high-efficient utilization of coal, concretely relates to system of well low temperature dry distillation raw coke oven gas through resistant sulphur samming methanation system LNG (liquefied natural gas).
Background
Natural gas, as a high-efficiency, clean and safe fossil energy, has increased year by year in global energy consumption; along with the enhancement of environmental awareness and the improvement of life quality of people, the demand of natural gas is increased year by year, coal resources with relatively rich reserves are utilized to deeply develop a low-temperature dry distillation natural gas co-production technology of low-quality coal, and raw gas with lower heat value is utilized to be converted into environment-friendly natural gas, so that the comprehensive utilization of the coal resources is realized, the phenomenon of relative shortage of oil and gas resources in China is relieved, and the clean and efficient utilization technical route of coal is met.
Three products, namely semi coke, coal tar and raw coke gas (also called semi coke tail gas or low-temperature carbonization gas) are obtained in the semi coke production process by low-quality coal low-temperature carbonizationThe produced raw gas components are shown in table 1, and it can be seen that the raw gas components have low methane content, low gas heat value, and contain a large amount of nitrogen, the energy consumption in the compression and liquefaction processes is high, the process cost for directly purifying methane from gas is high, the raw gas is generally combusted by a boiler to produce steam and generate electricity at present, and the economic benefit is low. The coal can generate a large amount of H in the low-temperature dry distillation process2CO and CO2But the hydrogen-carbon ratio (H/C) is about 1.8-2.2, which is not beneficial to methanation reaction, and also contains C2-C4 paraffin and olefin as main petroleum gas components, H2S、NH3And tar, dust, etc.
Table 1: crude gas component of traditional vertical furnace
With the development of the low-temperature dry distillation technology of pulverized coal in recent years, technologies such as an external heating type vertical furnace, a solid heat carrier low-temperature rapid pyrolysis technology, a pulverized coal rotary kiln pyrolysis technology and the like appear, the technology is different from the prior mode that flue gas is directly heated by adopting indirect heating, the produced raw coke oven gas has more effective combustible components, the general components of the raw coke oven gas are shown in a table 2, the content of nitrogen is obviously reduced, but the problems of low hydrogen-carbon ratio and high carbon dioxide content still exist.
Table 2: indirectly heated raw gas component for pyrolysis technology
Because of the characteristics of the raw coke oven gas, unlike the coke oven gas which is easy to prepare natural gas, the development of a technology for preparing natural gas by methanation, which is suitable for the raw coke oven gas, is urgently needed, and the technology can be used for preparing natural gas at a low H/C ratio and high CO2Under the condition of partial pressure, high CO conversion rate and high CH are realized4And (4) selectivity.
Disclosure of Invention
In order to solve the existing problems, the utility model aims to provide a system and method for preparing LNG through sulfur-resistant uniform temperature methanation of medium and low temperature dry distillation raw gas have realized the clean high-efficient utilization of low order coal, produce the liquefied natural gas of high calorific value and by-products such as by-product tar, LPG, sulphur, carbon dioxide, energy saving, economic benefits is high.
The utility model discloses a following technical scheme realizes:
the utility model discloses a system for well low temperature dry distillation raw coke oven gas is through resistant sulphur samming temperature methanation system LNG, including deamination dust collector, deamination dust collector's entry linkage has well low temperature dry distillation raw coke oven gas intake pipe, exit linkage has one-level compressor arrangement, one-level compressor arrangement is connected with the rectified oil recovery unit, rectified oil recovery unit is connected with the second grade compressor arrangement, the second grade compressor arrangement is connected with resistant sulphur methanation arrangement and liquefied petroleum gas collection device, resistant sulphur methanation arrangement is connected with the desulfurization decarbonization device, the desulfurization decarbonization device is connected with the dehydration adsorption tower, carbon dioxide collection device and hydrogen sulfide collection device, hydrogen sulfide collection device is connected with claus sulphur recovery unit, the dehydration adsorption tower is connected with the cryrogenic liquefaction device, the cryrogenic liquefaction device is connected with nitrogen gas collection device and LNG discharge pipe.
Preferably, the first-stage compression device is a screw compressor and the second-stage compression device is a piston compressor.
Preferably, the rectification oil recovery device is a rectification tower or a temperature swing adsorption device.
Preferably, an oxygen removal device is arranged between the rectification oil recovery device and the secondary compression device.
Preferably, the sulfur-resistant methanation device is a tubular uniform temperature reactor, a cobalt-molybdenum catalyst is arranged in a tube pass of the tubular uniform temperature reactor, and boiling water is 60-100 bar in a shell pass; the two ends of the tube pass are respectively connected with the secondary compression device and the desulfurization and decarburization device.
Further preferably, the shell side is connected with a steam drum, and the shell side, the steam drum, the rectified oil recovery device and the desulfurization and decarburization device form a closed circulation loop of boiling water/saturated steam.
Preferably, the desulfurization and decarbonization device comprises a desulfurization tower and a decarbonization tower which are filled with MDEA solution, the inlet of the decarbonization tower is connected with the sulfur-tolerant methanation device, the outlet of the decarbonization tower is connected with the inlet of the desulfurization tower and the dehydration adsorption tower, and the outlet of the desulfurization tower is connected with the hydrogen sulfide collection device.
Preferably, the tail gas discharge pipe of the cryogenic liquefaction device is connected with the sulfur-tolerant methanation device and the Claus sulfur recovery device.
Compared with the prior art, the utility model discloses following profitable technological effect has:
the utility model discloses a system for producing LNG by using middle and low temperature dry distillation raw gas through sulfur-resistant uniform temperature methanation, which recovers tar after dedusting, deamination and purification of the dry distillation raw gas to obtain a high-value byproduct; the high-grade hydrocarbons such as propane, butane and the like in the dry distillation coal gas are directly prepared into LPG through pressurization, liquefaction and separation, and simultaneously, a large amount of high-grade hydrocarbons are effectively utilized, so that the carbon load of a methanation section is greatly reduced, the thermal stability of the methanation catalyst is improved, and the service life of the methanation catalyst is prolonged. H desorbed from desulfurization and decarbonization device2The S gas has high purity, and sulfur can be recovered by adopting a Claus sulfur recovery process. CH in liquefied natural gas obtained after cryogenic liquefaction separation4The content is high and is more than 95 percent, and the requirement of a first-grade natural gas product is met. The low-temperature dry distillation poly-generation technology of coal is adopted, so that the clean and efficient utilization of low-rank coal is realized, the liquefied natural gas with high calorific value is produced, and byproducts such as tar, LPG, sulfur, carbon dioxide and the like are produced
Furthermore, the first-stage compression device is a screw compressor, the second-stage compression device is a piston compressor, the type of the compression device is selected according to actual needs, the arrangement is reasonable, and the cost is saved.
Furthermore, an oxygen removal device is arranged between the rectification oil recovery device and the secondary compression device, so that the activity of the catalyst in the subsequent reactor can be protected.
Furthermore, the sulfur-tolerant cobalt-molybdenum catalyst is adopted, the dual-function catalytic action of transformation and methanation is achieved, the traditional wet desulphurization and dry desulphurization process sections are omitted, the tubular reactor is adopted to replace the traditional multi-section heat-insulating fixed bed reactor, the process flow is shortened, and the equipment investment is saved; the combination of the sulfur-tolerant methanation catalyst and the temperature-equalizing tubular reactor controls the reaction temperature to be 300-400 ℃, thereby realizing the high CO conversion of the raw gas with low hydrogen-carbon ratioRate and high CH4Selectivity, solves the problems of low CO conversion rate and CO conversion at the high temperature of 650 ℃ in the traditional heat-insulating bed of 550-2High selectivity (high reaction rate at high temperature in water gas reaction).
Furthermore, the medium-pressure steam produced by the tubular reactor can provide heat for the rectification oil recovery device and the desulfurization and decarburization device, so that the optimal utilization of heat is realized, and the energy is saved.
Further, desulfurization and decarburization are carried out in one unit, and H can be removed simultaneously through an MDEA absorption tower2S and CO2Acid gas, for CO2At concentrations less than 30%, MDEA (diethanolamine) absorption desorption is more economical than PSA.
Furthermore, the tail gas of the cryogenic liquefaction device is hydrogen-rich gas, and can be supplied to a sulfur-tolerant methanation device and a Claus sulfur recovery device for use, so that energy is saved.
Drawings
FIG. 1 is a schematic view of the whole system for producing LNG by methanation of sulfur-resistant uniform temperature from middle and low temperature dry distillation raw gas.
In the figure: 1-a middle-low temperature dry distillation raw gas inlet pipe, 2-a deamination dust removal device, 3-a primary compression device, 4-a rectification oil recovery device, 5-a secondary compression device, 6-a sulfur-tolerant methanation device, 7-a desulfurization and decarbonization device, 8-a Claus sulfur recovery device, 9-a dehydration adsorption tower, 10-a cryogenic liquefaction device, 11-an LNG discharge pipe, 12-a liquefied petroleum gas collection device, 13-a hydrogen sulfide collection device, 14-a carbon dioxide collection device and 15-a nitrogen collection device.
Detailed Description
The invention will be described in further detail with reference to the following drawings and specific examples, which are intended to illustrate and not to limit the invention:
FIG. 1 shows a system for producing LNG by methanation of middle and low temperature dry distillation raw gas at a sulfur-resistant uniform temperature, which comprises a deamination dust collector 2, wherein the inlet of the deamination dust collector 2 is connected with a middle and low temperature dry distillation raw gas inlet pipe 1, the outlet of the deamination dust collector is connected with a primary compressor 3, the primary compressor 3 is connected with a rectified oil recovery device 4, and the rectified oil recovery device 4 can adopt a rectifying tower or a temperature swing adsorption device; the rectification oil recovery device 4 is connected with a secondary compression device 5, and a deaerating device can be arranged between the rectification oil recovery device 4 and the secondary compression device 5; the secondary compression device 5 is connected with a sulfur-resistant methanation device 6 and a liquefied petroleum gas collection device 12, the sulfur-resistant methanation device 6 is a tubular isothermal reactor, a cobalt-molybdenum catalyst is arranged in the tube pass of the tubular isothermal reactor, and boiling water is 60-100 bar in the shell pass; the two ends of the tube pass are respectively connected with a secondary compression device 5 and a desulfurization and decarburization device 7. The shell pass is connected with a steam drum, and the shell pass, the steam drum, the rectified oil recovery device 4 and the desulfurization and decarburization device 7 form a closed circulation loop of boiling water/saturated steam.
Sulphur-resistant methanation device 6 is connected with desulfurization decarbonization device 7, and desulfurization decarbonization device 7 is including filling desulfurizing tower and the decarbonization tower of MDEA solution, and the import and the sulphur-resistant methanation device 6 of decarbonization tower are connected, and the export is connected with the import and the dehydration adsorption tower 9 of desulfurizing tower, and the export and the hydrogen sulfide collection device 13 of desulfurizing tower are connected.
The hydrogen sulfide collection device 13 is connected with a Claus sulfur recovery device 8, the desulfurization and decarbonization device 7 is connected with a dehydration adsorption tower 9, the dehydration adsorption tower 9 is connected with a cryogenic liquefaction device 10, the cryogenic liquefaction device 10 is connected with a nitrogen collection device 15 and an LNG discharge pipe 11, and a tail gas discharge pipe of the cryogenic liquefaction device 10 is connected with a sulfur-tolerant methanation device 6 and the Claus sulfur recovery device 8.
Screw compressor can be selected for use to one-level compressor arrangement 3, and piston compressor can be selected for use to second grade compressor arrangement 5.
The utility model discloses a system of well low temperature dry distillation raw coke oven gas through resistant sulphur samming methanation system LNG at the during operation:
the medium-low temperature dry distillation raw gas enters a deamination dust removal device 2 from a medium-low temperature dry distillation raw gas inlet pipe 1, ammonia gas is removed by washing, dust is removed by filtering, the gas enters a primary compression device 3, the gas enters a refined distillate oil recovery device 4 after being pressurized to 4-6 bar, components such as benzene, anthracene oil and tar in the gas are recovered, and the content of the benzene and the tar in the recovered gas components is less than 5 ppm.
The residual gas enters a secondary compression device 5, the secondary compression device 5 pressurizes the gas to 26-30 bar, liquefied petroleum gas components such as ethane, ethylene, propane, propylene, butane and butylene are changed into liquid in the compression process, and the byproduct liquefied petroleum gas enters a liquefied petroleum gas collecting device 12.
And the residual gas enters a sulfur-tolerant methanation device 6, the sulfur-tolerant methanation device 6 adopts a tubular temperature-equalizing reactor, a catalyst is filled in a tube pass, boiling water of 60-100 bar flows away from a shell pass, and natural circulation of a steam drum and the reactor is formed through the density difference of the boiling water. The catalyst adopts cobalt-molybdenum catalyst, and is treated by H in raw material gas2S is reduced to generate active MoS at low airspeed2The water gas shift reaction and the methanation reaction can be simultaneously realized. Because the hot spot temperature of the tubular temperature equalizing reactor is about 400 ℃, the outlet temperature is 260-280 ℃, CO in the raw coke oven gas is basically and completely converted, and the selectivity of methane is more than 85%. If the raw material gas is the raw gas of the traditional vertical furnace, the main components of the gas after the reaction of the sulfur-tolerant methanation device 6 are as follows: CH (CH)412-18% of CO, 0-0.3% of H23-6% of CO212-18% of N240-50% of H2O content of 6-12%, CnHm(ethane, ethylene, propane, propylene, butane, butylene) content is 0.5-5%, H2S content of 500-3000 ppm and NH3The content is 300-1200 ppm. If the raw gas is low-temperature dry distillation raw gas generated by external heating type vertical furnace, solid heat carrier low-temperature fast pyrolysis and pulverized coal rotary kiln pyrolysis, the main components of the gas after the reaction of the sulfur-resistant methanation device 6 are as follows: CH (CH)445-55% of CO, 0-0.3% of H23-6% of CO28-12% of N20 to 20% of H2O content of 6-24%, CnHm(ethane, ethylene, propane, propylene, butane, butylene) content is 0.5-6%, H2The S content is 500-3000 ppm. In addition, organic sulfur and SO in raw gas2Also converted to H by catalytic hydrogenation2And S. Each 1000-square raw material gas is methanated by a sulfur-tolerant methanation device 6 to produce a byproduct of saturated steam with the pressure of 1.2-2.5 tons and the pressure of 60-100 bar, and the saturated steam can be used for heating the solution of a desulfurization and decarbonization device 7The rectification or temperature swing adsorption of the desorption and rectification oil recovery device 4 realizes the optimized utilization of heat.
The main reactions that occur during methanation are as follows:
CO+3H2→CH4+H2O ΔH298K＝-206KJ/mol R1
CO2+4H2→CH4+2H2O ΔH298K＝-165KJ/mol R2
CO+H2O→H2+CO2ΔH298K＝-41.2KJ/mol R3
according to the reaction formula, the reactions of R1 and R2 are strong exothermic reactions, the temperature rise of 72 ℃ is brought by every 1% of CO converted, and every 1% of CO converted2The temperature rise of 60 ℃ can be brought, the reaction activity is highest at about 300 ℃, the reaction rate equilibrium constant is smaller when the temperature is higher, and the reaction driving force is smaller. At present, the methanation process generally adopts a method of using a multi-section adiabatic reactor and gas circulation to dilute the content of CO in raw material gas, the first section of the adiabatic fixed bed methanation reactor usually reaches 620-650 ℃, the reactions of R1, R2 and R3 reach thermodynamic equilibrium at the temperature, and CO react2And CH4The content is controlled by thermodynamic equilibrium, the conversion rate of CO is lower, a plurality of adiabatic reactors are subsequently added to ensure the reaction depth, and finally the CO content is lower than 0.1%. And a tubular isothermal reactor is adopted, a tube pass is filled with a catalyst, a shell pass adopts boiling water for heat exchange to timely remove heat released by the reaction from the reactor, and medium-pressure steam is a byproduct. The tubular temperature equalizing reactor can control the reaction temperature to be 300-400 ℃, the R1 reaction equilibrium constant is large in the temperature range, and the high conversion rate of CO can be realized in a section of reactor after the reaction is continuously carried out.
After reaction, the reaction product enters a desulfurization and decarbonization device 7, and H is dissolved in MDEA (diethanolamine) solution under high pressure through physical dissolution and chemical absorption2S and CO2Dissolving or generating intermediate, decompressing and flashing in a decarbonizing tower to separate out high-purity CO2Then high-purity H is resolved by heating solution in a desulfurizing tower2And S. CO at the outlet of the desulfurization and decarbonization device 72Absorption rate of about 95%, H2Removal of SThe rate is more than 99 percent.
High-purity H separated by the desulfurization and decarbonization device 72S enters a hydrogen sulfide collecting device 13 and then enters a Claus sulfur recovery device 8 to react to generate sulfur, and CO separated by a desulfurization and decarbonization device 72Entering the carbon dioxide collection device 14; residual gas in the desulfurization and decarbonization device 7 enters a dehydration adsorption tower 9 to remove moisture, then enters a cryogenic liquefaction device 10 to be compressed and liquefied, nitrogen separated after temperature reduction enters a nitrogen collection device 15, LNG passes through an LNG discharge pipe to be output to a system, and CH in the LNG4The content is more than 95 percent, and the tail gas of the cryogenic liquefying device 10 is hydrogen-rich gas which can be supplied to the sulfur-tolerant methanation device 6 and the Claus sulfur recovery device 8 for use.
It should be noted that the above description is only one of the embodiments of the present invention, and all equivalent changes made by the system described in the present invention are included in the protection scope of the present invention. The technical field of the present invention can be replaced by other embodiments described in a similar manner, without departing from the structure of the present invention or exceeding the scope defined by the claims, which belong to the protection scope of the present invention.
Claims (8)
1. A system for preparing LNG (liquefied natural gas) from middle-low temperature dry distillation raw gas through sulfur-resistant uniform-temperature methanation is characterized by comprising a deamination dust removal device (2), wherein an inlet of the deamination dust removal device (2) is connected with a middle-low temperature dry distillation raw gas inlet pipe (1), an outlet of the deamination dust removal device is connected with a primary compression device (3), the primary compression device (3) is connected with a rectified oil recovery device (4), the rectified oil recovery device (4) is connected with a secondary compression device (5), the secondary compression device (5) is connected with a sulfur-resistant methanation device (6) and a liquefied petroleum gas collection device (12), the sulfur-resistant methanation device (6) is connected with a desulfurization and decarbonization device (7), the desulfurization and decarbonization device (7) is connected with a dehydration adsorption tower (9), a carbon dioxide collection device (14) and a hydrogen sulfide collection device (13), and the hydrogen sulfide collection device (13) is connected with, the dehydration adsorption tower (9) is connected with a cryogenic liquefaction device (10), and the cryogenic liquefaction device (10) is connected with a nitrogen collection device (15) and an LNG discharge pipe (11).
2. The system for preparing LNG through sulfur-resistant uniform-temperature methanation of the medium-low-temperature dry distillation raw gas as claimed in claim 1, wherein the first-stage compression device (3) is a screw compressor, and the second-stage compression device (5) is a piston compressor.
3. The system for preparing LNG through sulfur-tolerant uniform temperature methanation of the medium-low temperature dry distillation raw gas as claimed in claim 1, wherein the rectification oil recovery device (4) is a rectification tower or a temperature swing adsorption device.
4. The system for preparing LNG through sulfur-resistant uniform temperature methanation of the medium and low temperature dry distillation raw gas as claimed in claim 1, wherein a deoxygenation device is arranged between the rectified oil recovery device (4) and the secondary compression device (5).
5. The system for preparing LNG through sulfur-resistant uniform-temperature methanation of the medium-low-temperature dry distillation raw gas as claimed in claim 1, wherein the sulfur-resistant methanation device (6) is a tubular uniform-temperature reactor, a cobalt-molybdenum catalyst is arranged in a tube pass of the tubular uniform-temperature reactor, and boiling water is 60-100 bar in a shell pass; two ends of the tube pass are respectively connected with a secondary compression device (5) and a desulfurization and decarburization device (7).
6. The system for preparing LNG through sulfur-tolerant uniform-temperature methanation of the medium-low-temperature dry distillation raw gas as claimed in claim 5, wherein a steam drum is connected to a shell side, and the shell side, the steam drum, the rectification oil recovery device (4) and the desulfurization and decarburization device (7) form a closed circulation loop of boiling water/saturated steam.
7. The system for preparing LNG through sulfur-resistant uniform-temperature methanation of the medium-low-temperature dry distillation raw gas as claimed in claim 1, wherein the desulfurization and decarbonization device (7) comprises a desulfurization tower and a decarbonization tower which are filled with MDEA solution, an inlet of the decarbonization tower is connected with the sulfur-resistant methanation device (6), an outlet of the decarbonization tower is connected with an inlet of the desulfurization tower and the dehydration adsorption tower (9), and an outlet of the desulfurization tower is connected with the hydrogen sulfide collection device (13).
8. The system for preparing LNG through sulfur-tolerant uniform temperature methanation of the medium-low temperature dry distillation raw gas as claimed in claim 1, wherein a tail gas discharge pipe of the cryogenic liquefaction device (10) is connected with the sulfur-tolerant methanation device (6) and the Claus sulfur recovery device (8).
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