CN112897464B - Process for producing hydrogen and coproducing LNG (liquefied natural gas) by using raw gas with methanation - Google Patents
Process for producing hydrogen and coproducing LNG (liquefied natural gas) by using raw gas with methanation Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
Abstract
The invention provides a process for producing hydrogen and coproducing LNG by using raw gas with methanation, and belongs to the technical field of raw gas hydrogen production. The process takes the raw coke oven gas obtained by pyrolyzing the low-rank coal as a raw material, and high-purity hydrogen and LNG products are obtained through pretreatment, compression purification, conversion hydrogenation, desulfurization and decarbonization, methanation, pressure swing adsorption and cryogenic separation. According to the invention, the tar and naphthalene multi-stage removal system is arranged in the process of hydrogen production and LNG co-production of raw coke oven gas, and impurities such as tar, naphthalene, ammonia and sulfur can be effectively removed under the condition that the impurities in the raw coke oven gas fluctuate in a large range through the optimized combination of all purification processes. The process of the invention is provided with methanation, and the LNG productivity can be increased by 40-60% under the condition of the same raw gas amount and hydrogen yield. Meanwhile, the concentration of methane in the raw coke oven gas is increased from about 6% to 11-24% through methanation, and is further concentrated to 24-60% through PSA, so that the gas amount entering cryogenic separation is greatly reduced, and the investment and energy consumption of the cryogenic separation are greatly reduced.
Description
Technical Field
The invention belongs to the technical field of raw gas hydrogen production, and particularly relates to a process for producing hydrogen and coproducing LNG by using raw gas with methanation.
Background
The basic characteristics of energy resources in China are rich coal, poor oil and little gas, and the coal resources occupy the main position of energy structures in China for a long time. The method for producing oil gas by using coal relieves the shortage of oil gas resources in China, meets the requirements of national economy and people's life on fuel oil and fuel gas, becomes the important requirement of national energy strategy, and is also one of the key development directions of clean coal technology, especially coal conversion technology in future in China. Considering that more than 55% of the total storage amount of coal in China is low-rank coal comprising lignite, subbituminous coal and the like, the hydrogen-carbon ratio in the coal structure is relatively high, oil gas and chemicals can be directly converted and extracted under a mild pyrolysis condition, and the residual semicoke is used as a combustion fuel or a gasification raw material. Therefore, the grading utilization of the low-rank coal through pyrolysis has important significance for solving the national important requirements and realizing the clean high-valued utilization of the coal in China. The low-rank coal pyrolysis technology can be generally divided into an internal heating type pyrolysis technology and an external heating type pyrolysis technology, the internal heating type pyrolysis technology is more and more mature in industrial application at present, and the external heating type pyrolysis technology is still in a research and demonstration stage.
The internal heating type low-rank coal pyrolysis raw gas is characterized in that the nitrogen content is high and is generally more than 40%. In addition, the raw gas has complex impurity components and wide content distribution. The raw gas can be used as fuel and for power generation, and can also be purified to separate out the effective components of hydrogen, CO and methane, the hydrogen and CO can be used as downstream devices, such as raw materials for tar hydrogenation or organic synthesis, and the methane can be made into SNG, CNG or LNG for sale.
Unit technologies used for raw gas purification and separation, such as horizontal pipe cooling, electric tar capture, compression, wet desulphurization, transformation, pressure swing adsorption, methanation, cryogenic separation and the like, are mature technologies, and the difficulty lies in how to combine the technologies, how to ensure the reliability and stability of the device, and how to reduce the investment and the operating cost as much as possible.
The raw gas has low methane content, the refrigeration process is poor in economy, and the requirement on purification of impurities in the raw gas is high (under the same LNG yield, the lower the methane concentration in the raw gas is, the larger the total gas amount in the cooling box is, and the higher the requirement on the impurity content is). Therefore, the key points of the raw gas purification and separation are as follows: 1) the reliability of tar and naphthalene removal ensures the continuous and stable long-period operation of the device; 2) large PSA adsorbent packing amount, high replacement cost, high requirement of cryogenic unit for impurity purification, and high CO content2Sulfur, hydrocarbons above C5, ammonia, etc. all tend to cause cold box blockage. Therefore, the cleaner the gas entering the PSA unit and the cryogenic unit, the simpler the composition, the better. 3) The concentration of methane in the feed gas of the cryogenic separation unit is improved as much as possible, the compression energy consumption is reduced, and the investment and the energy consumption of the cryogenic separation unit are also reduced.
Disclosure of Invention
The invention aims to provide a process for producing hydrogen and coproducing LNG (liquefied natural gas) by using raw coke oven gas with methanation2And multi-carbon hydrocarbon multi-turnThe conversion of the liquefied natural gas into methane not only increases the LNG yield, but also greatly simplifies the PSA hydrogen extraction and cryogenic separation process, reduces the investment of PSA and cryogenic separation devices and reduces the cost.
The purpose of the invention is realized by the following technical scheme:
the technology uses the raw gas obtained by low-rank coal pyrolysis as a raw material, and obtains high-purity hydrogen and LNG products through pretreatment, compression purification, conversion hydrogenation, desulfurization decarbonization, methanation, pressure swing adsorption and cryogenic separation:
the pretreatment comprises partial or all units of pressurization, cooling, electric tar capture, crude tar removal naphthalene and a gas holder;
the compression purification comprises a part or all of units in first-stage compression, cooling, wet desulphurization, temperature swing adsorption and second-stage compression;
the shift hydrogenation comprises a part or all of units in deoxidization, CO shift and organic sulfur hydroconversion;
the desulfurization and decarbonization comprises partial or all units in hydrogen sulfide removal, carbon dioxide removal, hydroconversion and fine desulfurization;
the methanation comprises part or all of units in heat exchange, methanation and cooling separation;
the pressure swing adsorption adopts two-section pressure swing adsorption, wherein 85-95% of methane in the pressure swing adsorption is adsorbed by one-section PSA, and high-purity hydrogen is obtained at the outlet of the second-section PSA;
and the cryogenic separation is to obtain an LNG product by compressing and drying the PSA desorption gas and then liquefying and separating the PSA desorption gas.
In the invention, the raw gas generated by pyrolyzing the low-rank coal is the raw gas obtained by primarily cooling the raw gas generated by pyrolyzing the coal and recovering tar, the temperature is 40-80 ℃, the pressure is 4-10 kPaG, and the typical dry basis composition is (volume percentage): 35 to 50 parts of nitrogen, 18 to 30 parts of hydrogen, 10 to 16 parts of carbon monoxide, 6 to 12 parts of carbon dioxide, 0.4 to 1.2 parts of oxygen, 1 to 4 parts of C2-C5 hydrocarbon, wherein the main impurity component is (mg/Nm)3): 300 of tar 2000, 300 of naphthalene 1000, 100 of ammonia 1000, 500 of hydrogen sulfide 1000, 100 of organic sulfur 300, 100 of hydrogen cyanide 300, C6 and above 300 of hydrocarbon 1000.
In the process, pretreatment and compression purification belong to the removal of tar naphthalene, wherein the crude tar naphthalene removal is carried out, one-section compression and temperature swing adsorption are necessary steps, and other units can be selectively arranged according to the temperature of the raw gas and the content of the tar naphthalene.
And further, the pretreatment comprises the steps of pressurizing the raw gas by a blower, then cooling the raw gas in a transverse pipe cooler, feeding the cooled raw gas into an electric tar precipitator, then feeding the cooled raw gas into a crude tar naphthalene remover to further remove tar and naphthalene, and finally feeding the raw gas into a gas holder.
Further, the upper section of the horizontal pipe cooler is cooled by normal-temperature circulating water, the temperature of the water on the normal-temperature circulating water is 30-32 ℃, and the raw coke oven gas is cooled to be below 45 ℃; the lower section of the horizontal pipe cooler is cooled by low-temperature circulating water, the temperature of the low-temperature circulating water is 5-13 ℃, the raw coke oven gas is cooled to 20-25 ℃, the electric tar precipitator is in two stages, and the total amount of tar naphthalene in the raw coke oven gas after passing through the crude tar naphthalene precipitator is less than 50mg/Nm3(ii) a The gas holder is a wet gas holder or a dry gas holder, and the pressure of the gas holder is 3-5 kPaG.
Further, the compression purification is to compress the raw gas from the gas holder to 0.3-0.8MPaG through one-stage compression, then cool the raw gas to 30-40 ℃ through circulating water, then separate the gas and the liquid, remove part of tar, naphthalene, dust and ammonia, cool the raw gas to 20-30 ℃ through low-temperature water at 5-13 ℃, and remove the tar and the naphthalene to 10mg/Nm3Then the raw gas enters a wet desulphurization unit to remove hydrogen sulfide in the raw gas to 20-50mg/Nm3Most of ammonia and hydrogen cyanide are removed; the crude gas after wet desulphurization enters a temperature swing adsorption unit to remove tar and naphthalene to 1mg/Nm3Hereinafter, most of ammonia and C6 and above hydrocarbons are removed simultaneously; the crude gas after temperature swing adsorption enters a second-stage compression, the crude gas is compressed to 1.0-3.0MPaG and then is subjected to a hydrogenation conversion process.
Further, the conversion hydrogenation is that the raw gas after the second-stage compression is preheated and then sequentially enters a deoxygenation reactor, a first-stage conversion reactor and a first-stage hydrogenation reactor, and then enters a second-stage conversion reactor after being recycled and heat exchanged, and the conversion gas is subjected to heat exchange, cooling and water separation and then is subjected to a desulfurization and decarburization process. Wherein, the first-stage shift reactor realizes first-stage CO shift, the hydrogenation reactor realizes organic sulfur hydrogenation conversion, and the second-stage shift reactor realizes second-stage CO shift.
The shift is preferably a sulfur tolerant adiabatic shift process, typically in a two-stage configuration, with a first hydrogenation reactor at the exit of the first-stage shift reactor to convert organic sulfur to hydrogen sulfide. If the size of the reactor allows, the first-stage shift reactor and the first-stage hydrogenation reactor can be combined into one reactor, the upper section of the reactor is provided with a shift catalyst, and the lower section of the reactor is provided with a hydrogenation catalyst. Under some conditions, the two-stage shift reactor may be bypassed if the first-stage shift is sufficient to meet the process requirements.
Further, the desulfurization and decarbonization are to send the shift gas into an absorption tower to remove CO2And hydrogen sulfide, wherein the desulfurized and decarbonized raw gas enters a secondary hydrogenation reactor through heat exchange, the residual organic sulfur is converted into hydrogen sulfide, and then the hydrogen sulfide enters fine desulfurization to remove the total sulfur to be below 0.1 ppm.
Further, the methanation reaction comprises the step that purified gas after fine desulfurization enters a methanation reactor after heat exchange, and CO in the purified gas2And the multi-carbon hydrocarbon is completely converted into methane, and the tail stage methanation outlet CO and CO are2The total amount is less than 20ppm, and the methanated gas enters a pressure swing adsorption process after cooling and water separation. In the methanation unit, all the hydrocarbons above C2 can be converted into methane, the conversion rate of the C2 hydrocarbon is more than 95%, and the conversion rate of the hydrocarbons above C3 is more than 99%; the raw gas after methanation mainly contains nitrogen, hydrogen, methane, saturated water and a small amount of C2 hydrocarbon.
Further, the methanation adopts an adiabatic methanation process, the methanation reactor is provided with 2-3 sections, a waste pot is arranged at the outlet of the first section of methanation reactor, the waste pot enters the second section of methanation reactor after heat recovery and temperature reduction to 350 ℃, part of gas at the outlet of the second section of methanation reactor enters a circulating gas compressor after heat exchange, the circulating gas is mixed with the first section of methanation purified gas, and the circulating gas amount is determined according to CO and CO in the raw gas2And (4) adjusting the quantity.
Methanation is an important means for adjusting the product yield, and can realize the free adjustment of hydrogen and LNG products under 0-100% of design load by matching with a conversion and decarburization unit. MethanationSimultaneously has the function of purifying CO and CO2And almost all the hydrocarbons above C3 are converted into methane, so that the PSA and cryogenic separation process is greatly simplified, and the investment and energy consumption are greatly reduced.
Furthermore, the pressure swing adsorption adopts a two-stage pressure swing adsorption process, most of methane is adsorbed by the first-stage PSA, desorbed gas is concentrated methane-rich gas, and hydrogen with the purity of more than 99.9V% is obtained at the outlet of the second-stage PSA.
Further, the cryogenic separation comprises the steps of compressing the primary PSA desorption gas by a desorption gas compressor, feeding the compressed desorption gas into a drying unit, removing water in the desorption gas by adopting a molecular sieve, and simultaneously removing CO in the desorption gas2And removing ammonia, feeding the dried desorption gas into a cold box, performing liquefaction separation by adopting a mixed refrigerant refrigeration separation process to obtain an LNG product, using the cryogenic tail gas part as dry regeneration gas, and discharging the rest.
The PSA adsorption is arranged according to two sections, and the main purposes of the PSA adsorption are to concentrate and enrich methane in the methanated gas as much as possible, improve the concentration of methane in the desorbed gas, reduce the gas flow of the cryogenic separation unit and reduce the investment and energy consumption of cryogenic separation (including desorbed gas compression). The adsorbent regeneration process is selected according to the hydrogen yield, and the flushing regeneration is selected as much as possible under the condition that the yield can be ensured, so that the energy consumption is reduced. If the raw gas quantity is limited and the hydrogen yield requirement exceeds the maximum yield which can be achieved by PSA, part or all of the second-stage PSA desorption gas needs to be recovered, and the specific operation is that part or all of the second-stage PSA desorption gas is taken, compressed to the pressure of the first-stage PSA, mixed with the methanated gas and then enters the first-stage PSA. If the pressure index of the hydrogen delivered outside exceeds the hydrogen pressure at the outlet of the second PSA, the purified gas at the outlet of the first PSA can be pressurized and then delivered into the second PSA, so that the hydrogen pressure at the outlet of the second PSA reaches the pressure required by the hydrogen delivered outside.
The cryogenic separation of the present invention is preferably a mixed refrigerant refrigeration (MRC) process. Because the methanation unit is arranged and the concentration is further increased by PSA, the concentration of methane in the gas entering the deep cooling unit can be increased to 24-60%, and the investment and energy consumption of cryogenic separation can be greatly reduced. The pressure of a first section of PSA desorption gas compression outlet can be freely adjusted, and the whole set is based on the principle that the unit LNG energy consumption is the lowest. When the desorption gas amount exceeds a certain value, the influence of investment needs to be considered, and the pressure of the first-stage desorption gas compression can be properly increased for reducing equipment investment.
In each step, except for the preferred screw compressor of the first-stage compression of the raw gas, other compression types are not limited, and the process requirements can be met. The compressor can be driven by a steam turbine or a motor.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention optimizes the raw gas purification process, is provided with the tar naphthalene multi-stage removal system, adapts to the condition that impurities in the raw gas fluctuate in a large range through the optimized combination of each purification process and the proper process parameter setting, enables the impurities such as tar, naphthalene, ammonia, sulfur and the like to be effectively removed, ensures the long-period stable operation of the device, prolongs the service life of the catalyst after the adsorbent and reduces the operation cost.
2. According to the invention, after the shift hydrogenation and the decarburization desulfurization and before the pressure swing adsorption, the methanation unit is arranged, and under the condition of the same crude gas amount and hydrogen yield, compared with the condition of not arranging the methanation unit, the LNG yield can be increased by 40-60%.
3. The methanated gas mainly contains nitrogen, hydrogen and methane, other impurities are few, the processes of the pressure swing adsorption unit and the cryogenic separation purification unit are greatly simplified, and long-period operation can be realized.
4. The methane concentration in the raw coke oven gas is increased from about 6% to 11-24% through methanation, and further concentrated to 24-60% through PSA, so that the gas amount entering cryogenic separation is greatly reduced, and the investment and energy consumption of the cryogenic separation are greatly reduced.
5. The methanation unit is matched with the conversion and decarburization to adjust the hydrogen-carbon ratio, so that the hydrogen and LNG amount can be freely adjusted within 0-100% of load, and the methanation unit can adapt to various working conditions and market change conditions. Particularly, when the downstream hydrogen demand is reduced, the LNG yield can be increased through methanation by adjusting the CO conversion rate, so that the load of the whole device is ensured, and the economy is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Raw gas at 60 ℃, 4kPaG of pressure and 150000Nm of gas3Dry basis consisting of nitrogen 44, hydrogen 24, carbon monoxide 12, carbon dioxide 12, methane 6, oxygen 1.0, CnHm1.0, and impurities consisting of (mg/Nm)3): tar 1000, naphthalene 500, ammonia 500, hydrogen sulfide 600, organic sulfur 200, hydrogen cyanide 200, C6 and above hydrocarbons 500.
The process for preparing hydrogen and co-producing LNG by using the raw gas comprises the following specific steps:
1. pretreatment: the raw gas is pressurized to 10kPaG by a blower and then enters a horizontal tube cooler, the upper section of the horizontal tube cooler is cooled to 40 ℃ by circulating cooling water, the lower section of the horizontal tube cooler is cooled by low-temperature circulating water at 7 ℃, the temperature is reduced to 23 ℃, and then the raw gas enters a two-stage electrical tar precipitator, the tar is reduced to 100mg/Nm3Naphthalene is reduced to 50mg/Nm3The pressure is reduced to 6kPaG, then the crude tar naphthalene remover is used for removing tar, and the tar is reduced to 30mg/Nm3Naphthalene is reduced to 15mg/Nm3And then wet gas holder with a gas holder pressure of 4 kPaG.
2. Compression and purification: raw gas from a gas holder enters a first-stage compression, the raw gas is compressed to 0.7MPaG by a screw compressor in the first-stage compression, the outlet temperature of the screw compressor acts at 40 ℃, the raw gas enters a cooling tower, the raw gas is cooled to 30 ℃ by low-temperature circulating water, and tar and naphthalene are reduced to 10mg/Nm3The ammonia is reduced to 150mg/Nm3. The cooled raw gas enters a wet desulphurization tower, and hydrogen sulfide is removed to 50mg/Nm by adopting a PDS desulphurization process3The desulfurization solution is regenerated to produce sulfur as a byproduct, and the wet desulfurization unit simultaneously removes ammonia to 50mg/Nm3The following. The desulfurized raw gas enters a 4-tower TSA unit (temperature swing adsorption unit), and tar and naphthalene are removed to 1mg/Nm3Ammonia is removed to 10mg/Nm3Removing the C6 and above multi-carbon hydrocarbon to 100mg/Nm3(ii) a The gas after temperature swing adsorption enters a two-stage compressor to be compressed to 1.65MPaG, and the two-stage compressor adopts centrifugal compressionA machine is provided.
3. And (3) shift hydrogenation: the raw coke oven gas after the second-stage compression enters a deoxygenation reactor after heat exchange is carried out to 210 ℃, oxygen is removed to be less than 30ppm, meanwhile, the temperature is raised to 340 ℃, steam is added according to a certain proportion, the raw coke oven gas enters a first-stage shift reactor after heat exchange is carried out to 250 ℃, the temperature of an outlet of the first-stage shift reactor is raised to 360 ℃, the raw coke oven gas enters a first-stage hydrogenation reactor, more than 90% of organic sulfur is converted into hydrogen sulfide, heat is recovered through a waste boiler, the temperature is reduced to 190 ℃, and then the raw coke oven gas enters a second-stage shift reactor. And (3) cooling the gas at the outlet of the two-stage shift reactor to 40 ℃ through multi-stage heat exchange, separating water, and then performing a desulfurization and decarburization process. CO conversion 0.95.
4. And (3) desulfurization and decarburization: the shift gas enters the absorber column at 1.45MPaG, and the MEDA solution converts CO in the shift gas2And removing H in the raw gas after decarbonization by using hydrogen sulfide2S≤10mg/Nm3，CO0.71％，CO20.1 percent, exchanging heat to 320 ℃, removing a secondary hydrogenation reactor, converting residual organic sulfur into hydrogen sulfide, then entering a fine desulfurization tank, removing the total sulfur to be below 0.1ppm by adopting zinc oxide, and then performing a demethanization process. The absorption liquid is heated and regenerated by steam, CO2The desorbed gas contains hydrogen sulfide of 900mg/Nm3And adopting PDS desulfurization and dry desulfurization to ensure that the content of the hydrogen sulfide reaches the emission standard and then is discharged.
5. Methanation: the purified gas enters a first-stage methanation reactor after being subjected to heat exchange to 300 ℃, and CO in the purified gas are2The total content is not high, and circulating gas can not be added. The outlet temperature of the first-stage methane reactor is about 360 ℃, the heat is recovered to 280 ℃ through the waste boiler and enters the second-stage methanation reactor, the outlet temperature of the second-stage methanation reactor is subjected to heat exchange and cooling to 40 ℃, the pressure is 1.2MPaG, and the methane concentration is increased from 7.04 percent to 11.04 percent (CO + CO)2Less than 20ppm), the total gas amount after methanation is 124254Nm3And h, entering a pressure swing adsorption unit. Part of the gas at the outlet of the two-stage methanation reactor enters a circulating gas compressor after heat exchange, the circulating gas is mixed with the first-stage methanation purified gas, and the circulating gas amount is determined according to CO and CO in the raw gas2And (4) adjusting the quantity.
6. Pressure swing adsorption: the methanation gas enters a first-stage pressure swing adsorption, and a first-stage PSA adsorbent is regenerated by flushingProcess, one-stage pressure swing adsorption stripping gas flow 47775Nm3The methane concentration was 26.93%. The purified gas of the first-stage PSA enters a second-stage PSA, the hydrogen purity at the outlet of the second-stage PSA is 99.91 percent, and the flow rate is 37501Nm3The pressure is 1.10MPaG, and the two-stage PSA adsorption regeneration adopts a vacuumizing process. The second-stage desorbed gas is used as temperature swing adsorption regenerated gas and then used as fuel. The hydrogen yield in the pressure swing adsorption process is 85.3 percent.
7. Cryogenic separation: the first-stage PSA desorption gas is compressed to 1.5MPaG and then enters a drying unit, the drying process adopts a decompression drying process, water is removed to below 1ppm through a molecular sieve, and part of ammonia and CO can be removed simultaneously2And removing to meet the index of entering a cold box. The cryogenic separation adopts a mixed refrigerant refrigeration process, the LNG yield is 9.06 tons/hour, and the methane yield is 96 percent. The deep cooling tail gas is used as dry regeneration gas, and the rest meets the emission standard and can be directly discharged.
This example was compared to the effect of no methanation, as in table 1 below:
table 1 comparison of example 1 with the effect of no methanation
Example 2
Raw gas at 60 ℃, 4kPaG of pressure and 150000Nm of gas3Dry basis consisting of (V%) nitrogen 44, hydrogen 24, carbon monoxide 12, carbon dioxide 12, methane 6.0, oxygen 1.0, CnHm1.0, and impurities (mg/Nm)3): tar 1000, naphthalene 500, ammonia 500, hydrogen sulfide 600, organic sulfur 200, hydrogen cyanide 200, C6 and above hydrocarbons 500.
The present example pertains to the shut-down of hydrogen users, and the total production of LNG is achieved by adjusting the CO conversion rate and by methanation. The method comprises the following specific steps:
1. pretreatment: the raw gas is pressurized to 10kPaG by a blower and then enters a horizontal tube cooler, the upper section of the horizontal tube cooler is cooled to 40 ℃ by circulating cooling water, the lower section of the horizontal tube cooler is cooled by low-temperature circulating water at 7 ℃, the temperature is reduced to 23 ℃, and then the raw gas enters a two-stage electrical tar precipitator, the tar is reduced to 100mg/Nm3Naphthalene is reduced to 50mg/Nm3The pressure is reduced to 6kPaG, then the crude tar naphthalene remover is used for removing tar, and the tar is reduced to 30mg/Nm3Naphthalene is reduced to 15mg/Nm3And then wet gas holder with a gas holder pressure of 4 kPaG.
2. Compression and purification: raw gas from a gas holder enters a first-stage compression, the raw gas is compressed to 0.7MPaG by a screw compressor in the first-stage compression, the outlet temperature of the screw compressor is 40 ℃, the raw gas enters a cooling tower, the raw gas is cooled to 30 ℃ by low-temperature circulating water, and tar and naphthalene are reduced to 10mg/Nm3The ammonia is reduced to 150mg/Nm3. The cooled raw gas enters a wet desulphurization tower, and hydrogen sulfide is removed to 50mg/Nm by adopting a PDS desulphurization process3The desulfurization solution is regenerated to produce sulfur as a byproduct, and the wet desulfurization unit simultaneously removes ammonia to 50mg/Nm3The following. The desulfurized raw gas enters a 4-tower TSA unit (temperature swing adsorption unit), and tar and naphthalene are removed to 1mg/Nm3Ammonia is removed to 10mg/Nm3Removing the C6 and above multi-carbon hydrocarbon to 100mg/Nm3(ii) a And the gas subjected to temperature swing adsorption enters a second-stage compressor to be compressed to 2.00MPaG, and the second-stage compressor adopts a centrifugal compressor.
3. And (3) shift hydrogenation: the raw coke oven gas after the second-stage compression enters an oxygen removal reactor after heat exchange is carried out to 210 ℃, oxygen is removed to be less than 30ppm, meanwhile, the temperature is raised to 340 ℃, steam is added according to a certain proportion, the heat exchange is carried out to 250 ℃ and then enters a first-stage shift reactor, the temperature of the outlet of the first-stage shift reactor is raised to 310 ℃, the temperature enters a first-stage hydrogenation reactor, more than 90 percent of organic sulfur is converted into hydrogen sulfide, the heat is recovered by a waste boiler, the water is separated after the temperature is cooled to 40 ℃ through multi-stage heat exchange, and then the processes of desulfurization and decarburization are carried out. CO conversion 0.44. A two-stage shift reactor bypass.
4. And (3) desulfurization and decarburization: the shift gas enters the absorption tower at 1.85MPaG, and the MEDA solution can enable CO in the shift gas2And the removal of the hydrogen sulphide is carried out,h in the decarbonized raw gas2S≤10mg/Nm3，CO7.9％，CO20.2 percent, exchanging heat to 320 ℃, removing a secondary hydrogenation reactor, converting residual organic sulfur into hydrogen sulfide, then entering a fine desulfurization tank, removing the total sulfur to be below 0.1ppm by adopting zinc oxide, and then performing a demethanization process. The absorption liquid is heated and regenerated by steam, CO2The desorbed gas contains hydrogen sulfide of 900mg/Nm3And adopting PDS desulfurization and dry desulfurization to ensure that the content of the hydrogen sulfide reaches the emission standard and then is discharged.
5. Methanation: purified gas enters a first-stage methanation reactor after being subjected to heat exchange to 260 ℃, and CO are generated2The content is high, and the circulating gas after the second-stage methanation is required to be added. The outlet temperature of the first-stage methane reactor is 480 ℃ below zero, the waste heat is recycled to 280 ℃ through a waste boiler, the waste heat enters a second-stage methanation reactor, the outlet temperature of the second-stage methanation reactor is subjected to heat exchange and cooling to 40 ℃, the outlet methane content is 23.94%, the pressure is 1.45MPaG, part of the waste heat is subjected to cryogenic separation, the other part of the waste heat enters a circulating gas compressor, the circulating gas is mixed with the first-stage methanation purified gas, and the circulation ratio (circulating gas/fresh gas) is 1.
6. The PSA process bypasses, and the working condition is that a hydrogen user stops producing hydrogen and does not produce hydrogen.
7. Cryogenic separation: flow 96107Nm3The second-stage methanation reaction gas cooled to 40 ℃ enters a drying unit, and the drying process adopts a pressure reduction drying process, so that water can be removed to below 1ppm, and part of ammonia and CO can be removed2And removing to meet the index of entering a cold box. The cryogenic separation adopts a mixed refrigerant refrigeration process, and the yield of LNG is 16.12 tons/hour. The cryogenic tail gas contains part of hydrogen and methane, and is used as dry regeneration gas and then used as fuel.
Example 3
Raw gas with 60 ℃ of temperature, 4kPaG of pressure and 115000Nm of gas amount3Dry basis consisting of nitrogen 44, hydrogen 24, carbon monoxide 12, carbon dioxide 12, methane 6, oxygen 1.0, CnHm1.0, and impurities consisting of (mg/Nm)3): tar 1000, naphthalene 500, ammonia 500, hydrogen sulfide 600, organic sulfur 200, hydrogen cyanide 200, C6 and above hydrocarbons 500.
The embodiment belongs to the condition that the raw gas quantity of raw gas is insufficient, and methanation is not carried out in order to ensure the hydrogen yield. The method comprises the following steps of (1) directly feeding the desulfurized and decarbonized gas into a PSA unit to extract hydrogen:
1. pretreatment: the raw gas is pressurized to 10kPaG by a blower and then enters a horizontal tube cooler, the upper section of the horizontal tube cooler is cooled to 40 ℃ by circulating cooling water, the lower section of the horizontal tube cooler is cooled by low-temperature circulating water at 7 ℃, the temperature is reduced to 23 ℃, and then the raw gas enters a two-stage electrical tar precipitator, the tar is reduced to 100mg/Nm3Naphthalene is reduced to 50mg/Nm3The pressure is reduced to 6kPaG, then the crude tar naphthalene remover is used for removing tar, and the tar is reduced to 30mg/Nm3Naphthalene is reduced to 15mg/Nm3And then wet gas holder with a gas holder pressure of 4 kPaG.
2. Compression and purification: raw gas from a gas holder enters a first-stage compression, the raw gas is compressed to 0.7MPaG by a screw compressor in the first-stage compression, the outlet temperature of the screw compressor is 40 ℃, the raw gas enters a cooling tower, the raw gas is cooled to 30 ℃ by low-temperature circulating water, and tar and naphthalene are reduced to 10mg/Nm3The ammonia is reduced to 150mg/Nm3. The cooled raw gas enters a wet desulphurization tower, and hydrogen sulfide is removed to 50mg/Nm by adopting a PDS desulphurization process3The desulfurization solution is regenerated to produce sulfur as a byproduct, and the wet desulfurization unit simultaneously removes ammonia to 50mg/Nm3The following. The desulfurized raw gas enters a 4-tower TSA unit, and tar and naphthalene are removed to 1mg/Nm3Ammonia is removed to 10mg/Nm3Removing the C6 and above multi-carbon hydrocarbon to 100mg/Nm3(ii) a The gas after temperature swing adsorption enters a second-stage compressor to be compressed to 1.65MPaG, and the second-stage compressor adopts a centrifugal compressor.
3. And (3) shift hydrogenation: the raw coke oven gas after the second-stage compression enters a deoxygenation reactor after heat exchange is carried out to 210 ℃, oxygen is removed to be less than 30ppm, meanwhile, the temperature is raised to 340 ℃, steam is added according to a certain proportion, the raw coke oven gas enters a first-stage shift reactor after heat exchange is carried out to 250 ℃, the temperature of an outlet of the first-stage shift reactor is raised to 360 ℃, the raw coke oven gas enters a first-stage hydrogenation reactor, more than 90% of organic sulfur is converted into hydrogen sulfide, heat is recovered through a waste boiler, the temperature is reduced to 190 ℃, and then the raw coke oven gas enters a second-stage shift reactor. And (3) cooling the gas at the outlet of the two-stage shift reactor to 40 ℃ through multi-stage heat exchange, separating water, and then performing a desulfurization and decarburization process. CO conversion 0.95.
4. And (3) desulfurization and decarburization:the shift gas enters the absorber at 1.45MPaG, and the MEDA solution can convert CO in the shift gas2And removing H in the raw gas after decarbonization by using hydrogen sulfide2S≤10mg/Nm3，CO0.71％，CO20.1%, because methanation is not required, fine desulfurization is not required, and the hydroconversion and fine desulfurization units can be bypassed. CO 22And (3) adopting PDS desulfurization and dry desulfurization in the desorption gas to ensure that the content of the hydrogen sulfide reaches the emission standard and then discharging.
5. And a fine desulfurization unit and a methanation unit bypass.
6. Pressure swing adsorption: the first-stage PSA adopts vacuumizing regeneration, the second-stage PSA adopts flushing regeneration, and due to insufficient gas quantity, in order to ensure the hydrogen yield, the second-stage desorption gas is mixed with the decarbonization gas and enters the first-stage PSA after being completely compressed to 1.40MPaG, and the total yield of the hydrogen is 96.6%. The hydrogen production was 37500Nm, as in example 13H, hydrogen pressure 1.30 MPaG.
7. Cryogenic separation: since the methane concentration in the first PSA desorption was 11.38%, the total amount was 7073Nm3The composition is used for producing LNG, and has the advantages of high power consumption, low yield (4.6 t/h) and high LNG production cost. Therefore, no LNG is produced under this extreme condition. PSA desorption gas is completely fed into a gas pipe network as raw material.
Example 4
Raw gas at 40 ℃, pressure of 8kPaG and gas amount of 150000Nm3Dry basis consisting of nitrogen 44, hydrogen 24, carbon monoxide 12, carbon dioxide 12, methane 6, oxygen 1.0, CnHm1.0, and impurities consisting of (mg/Nm)3): tar 300, naphthalene 200, ammonia 200, hydrogen sulfide 300, organosulfur 150, hydrogen cyanide 100, C6 and above hydrocarbons 300.
The embodiment is that hydrogen user production load reduces, and the hydrogen quantity reduces, reduces to 57% of normal load, through transform and methanation cooperation, can produce LNG with surplus CO and hydrogen more, in addition, because certain purification measure has been taken to the feed gas supply arrangement front end, partial impurity content of feed gas reduces to some extent, and concrete step is as follows:
1. pretreatment: because the pressure is enough, the blower is not needed for pressurization. The raw gas directly enters a horizontal pipe cooler and is cooled to 23 ℃ by using circulating water at the low temperature of 7 DEG CThen the tar is reduced to 100mg/Nm by a first-level electrical tar precipitator3Naphthalene is reduced to 50mg/Nm3The pressure is reduced to 5kPaG, the tar enters a crude tar naphthalene remover, and the tar is reduced to 30mg/Nm3Naphthalene is reduced to 15mg/Nm3And then a wet gas holder with a gas holder pressure of 3 kPaG.
2. Compression and purification: the first stage of compression is carried out by adopting a screw compressor to compress the mixture to 0.7MPaG, and the mixture is cooled to 25 ℃ by using low-temperature circulating water, so that wet desulphurization is not needed due to low content of hydrogen sulfide. The raw gas after screw compression enters a 4-tower TSA unit, and tar and naphthalene are removed to 1mg/Nm3Ammonia is removed to 10mg/Nm3Removing the C6 and above multi-carbon hydrocarbon to 100mg/Nm3(ii) a And the gas subjected to temperature swing adsorption enters a second-stage compressor to be compressed to 1.65MPaG, and the second-stage compressor adopts a centrifugal compressor.
3. And (3) shift hydrogenation: the raw coke oven gas after the second-stage compression enters an oxygen removal reactor after heat exchange is carried out to 210 ℃, oxygen is removed to be less than 30ppm, meanwhile, the temperature is raised to 340 ℃, steam is added according to a certain proportion, the heat exchange is carried out to 250 ℃ and then enters a first-stage shift reactor, the temperature of the outlet of the first-stage shift reactor is raised to 330 ℃, the temperature enters a first-stage hydrogenation reactor, more than 90 percent of organic sulfur is converted into hydrogen sulfide, the heat is recovered by a waste boiler, the water is separated to be subjected to a desulfurization and decarburization process after being cooled to 40 ℃ through multi-stage heat exchange, and the CO conversion rate is 0.7.
4. And (3) desulfurization and decarburization: the shift gas enters the absorption tower at 1.55MPaG, and the MEDA solution can enable CO in the shift gas2And removing H in the raw gas after decarbonization by using hydrogen sulfide2S≤10mg/Nm3，CO4.24％，CO20.1 percent, exchanging heat to 320 ℃, removing a secondary hydrogenation reactor, converting residual organic sulfur into hydrogen sulfide, then entering a fine desulfurization tank, removing the total sulfur to be below 0.1ppm by adopting zinc oxide, and then performing a demethanization process. The absorption liquid is heated and regenerated by steam, CO2And (3) desulfurizing the desorption gas by adopting a PDS desulfurization method and a dry desulfurization method to ensure that the content of the hydrogen sulfide reaches the emission standard and then discharging.
5. Methanation: the inlet temperature of the first-stage methanation reactor is 260 ℃, the circulating gas after second-stage methanation needs to be added, the circulating ratio (circulating gas/fresh gas) is 0.5, the methane content of the second-stage methanation outlet is 16.45 percent, and the pressure is 1.3 MPaG.
6、The methanated gas enters a first-stage pressure swing adsorption, and the first-stage pressure swing adsorption desorbs gas 51500Nm3H, the methane concentration is 33.25%; the purity of hydrogen at the outlet of the two-stage PSA is 99.9 percent, the pressure is 1.2MPaG, and the flow is 21516Nm3H is used as the reference value. The total yield of hydrogen in the pressure swing adsorption process of the temperature swing adsorption regeneration by using the two-stage desorbed gas is 82.8 percent.
Under the working condition, the raw gas is sufficiently supplied, but the hydrogen consumption is reduced to 57% of the design consumption, and the surplus raw gas can be adjusted through transformation, decarburization and methanation to produce LNG.
7. Cryogenic separation: and compressing the first-stage pressure swing adsorption stripping gas to 1.5MPaG, then feeding the gas into a drying unit, and carrying out cryogenic separation to obtain an LNG product with the LNG yield of 12 tons/hour. Under the same amount of raw gas, the LNG production increased 32.5% over the hydrogen full load regime (example 1).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The technology is characterized in that raw gas obtained by pyrolyzing low-rank coal is used as a raw material, and high-purity hydrogen and LNG products are obtained through pretreatment, compression purification, conversion hydrogenation, desulfurization and decarbonization, methanation, pressure swing adsorption and cryogenic separation:
the pretreatment comprises partial or all units of pressurization, cooling, electric tar capture, crude tar removal naphthalene and a gas holder;
the compression purification comprises a part or all of units in first-stage compression, cooling, wet desulphurization, temperature swing adsorption and second-stage compression;
the shift hydrogenation comprises a part or all of units in deoxidization, CO shift and organic sulfur hydroconversion;
the desulfurization and decarbonization comprises partial or all units in hydrogen sulfide removal, carbon dioxide removal, hydroconversion and fine desulfurization;
the methanation comprises part or all of units in heat exchange, methanation and cooling separation;
the pressure swing adsorption adopts two-section pressure swing adsorption, wherein 85-95% of methane in the pressure swing adsorption is adsorbed by one-section PSA, and high-purity hydrogen is obtained at the outlet of the second-section PSA;
and the cryogenic separation is to obtain an LNG product by compressing and drying the PSA desorption gas and then liquefying and separating the PSA desorption gas.
2. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the pretreatment comprises the steps of pressurizing the raw gas by a blower, cooling the raw gas in a horizontal pipe cooler, feeding the cooled raw gas into an electric tar precipitator, feeding the cooled raw gas into a crude tar and naphthalene remover to further remove tar and naphthalene, and finally feeding the raw gas into a gas holder.
3. The process for producing hydrogen and coproducing LNG from raw coke oven gas through methanation as claimed in claim 2, wherein the upper section of the horizontal tube cooler is cooled by normal-temperature circulating water, the temperature of the water on the normal-temperature circulating water is 30-32 ℃, and the raw coke oven gas is cooled to below 45 ℃; the lower section of the horizontal pipe cooler is cooled by low-temperature circulating water, the temperature of the low-temperature circulating water is 5-13 ℃, and the raw coke oven gas is cooled to 20-25 ℃; the electric tar precipitator is two-stage, and the total amount of tar and naphthalene in the crude gas after passing through the crude tar and naphthalene remover is less than 50mg/Nm3(ii) a The gas holder is a wet gas holder or a dry gas holder, and the pressure of the gas holder is 3-5 kPaG.
4. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the compression and purification are performed by compressing the raw gas from a gas holder to 0.3-0.8MPaG through one-stage compression, cooling the raw gas to 30-40 ℃ through circulating water, performing gas-liquid separation, removing part of tar, naphthalene, dust and ammonia, cooling the raw gas to 20-30 ℃ through 5-13 ℃ low-temperature water, and removing the tar and the naphthalene to 10mg/Nm3Then the raw gas enters a wet desulphurization unit to remove hydrogen sulfide in the raw gas to 20-50mg/Nm3Most of ammonia and hydrogen cyanide are removed; the crude gas after wet desulphurization enters a temperature swing adsorption unit to remove tar and naphthalene to 1mg/Nm3Hereinafter, most of ammonia andremoving C6 and above hydrocarbons; the crude gas after temperature swing adsorption enters a second-stage compression, the crude gas is compressed to 1.0-3.0MPaG and then is subjected to a hydrogenation conversion process.
5. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the shift hydrogenation is to preheat the raw gas after the second stage compression, then enter the deoxygenation reactor, the first stage shift reactor and the first stage hydrogenation reactor in sequence, then enter the second stage shift reactor after recovery and heat exchange, and remove the sulfur and carbon from the shifted gas after heat exchange, cooling and water separation.
6. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the desulfurization and decarbonization are carried out by sending the shift gas into an absorption tower to remove CO2And hydrogen sulfide, wherein the desulfurized and decarbonized raw gas enters a secondary hydrogenation reactor through heat exchange, the residual organic sulfur is converted into hydrogen sulfide, and then the hydrogen sulfide enters fine desulfurization to remove the total sulfur to be below 0.1 ppm.
7. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the methanation is carried out by exchanging heat on purified gas after fine desulfurization, and then feeding the purified gas into a methanation reactor, wherein CO and CO in the purified gas2And the multi-carbon hydrocarbon is completely converted into methane, and the CO are discharged from the end stage methanation2The total content is less than 20ppm, and the methanated gas enters a pressure swing adsorption process after cooling and water separation.
8. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 7, wherein the methanation adopts an adiabatic methanation process, the methanation reactor is provided with 2-3 sections, a waste pot is arranged at the outlet of the first-section methanation reactor, the waste pot recovers heat and reduces the temperature to 350 ℃ and then enters the second-section methanation reactor, part of the gas at the outlet of the second-section methanation reactor enters a recycle gas compressor after heat exchange, the recycle gas is mixed with the first-section methanation purified gas, and the recycle gas amount is determined according to CO and CO in the raw gas2And (4) adjusting the quantity.
9. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the pressure swing adsorption adopts a two-stage pressure swing adsorption process, the first-stage PSA adsorbs most of methane, desorbed gas is concentrated methane-rich gas, and hydrogen with purity of more than 99.9V% is obtained at an outlet of the second-stage PSA.
10. The process for producing hydrogen and coproducing LNG from raw gas with methanation as claimed in claim 1, wherein the cryogenic separation comprises the steps of compressing a section of PSA desorption gas by a desorption gas compressor, feeding the compressed desorption gas into a drying unit, removing water in the desorption gas by using a molecular sieve, and removing CO in the desorption gas2And removing ammonia, feeding the dried desorption gas into a cold box, performing liquefaction separation by adopting a mixed refrigerant refrigeration separation process to obtain an LNG product, using the cryogenic tail gas part as dry regeneration gas, and discharging the rest.
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| CN113321181A (en) * | 2021-07-09 | 2021-08-31 | 昆明理工大学 | Improved method for preparing ammonia synthesis gas by washing tail gas with liquid nitrogen |
| CN114149837B (en) * | 2021-10-29 | 2022-11-15 | 西南化工研究设计院有限公司 | Process for preparing liquefied natural gas and co-producing liquid ammonia or hydrogen by coke oven gas with conversion decarburization |
| CN114774170A (en) * | 2022-05-13 | 2022-07-22 | 宁夏渝丰化工股份有限公司 | Process method for preparing LNG and hydrogen by coke oven gas |
| CN115888313A (en) * | 2022-11-11 | 2023-04-04 | 西南化工研究设计院有限公司 | Productivity adjusting process for producing fuel cell hydrogen and pipeline natural gas by coke oven gas |
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