CN104017620B - The processing method of charing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas - Google Patents
The processing method of charing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas Download PDFInfo
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Abstract
The present invention relates to a kind of processing method carbonizing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas.Current enterprise is abundant not for the utilization of charing furnace gas, not only works the mischief to environment, and runs counter to the environment protection significance of energy-saving and emission-reduction.The present invention filters charing furnace gas, compresses, isolate nitrogen after deoxidation treatment, with hydrogen compress pressurize after also obtain liquefied ammonia further at ammonia synthesis converter synthetic ammonia; Adopt wide temperature sulfur resistant conversion process to regulate the volume ratio of hydrogen and carbon monoxide again, make organosulfur be transformed into hydrogen sulfide simultaneously; Carry out desulfurization and decarburization process again; Adopt multistage methanation reaction, obtain the gaseous mixture based on methane; Molecular sieve is used to remove moisture and carbonic acid gas; Liquefaction obtains the methane being greater than 99.5% purity.The present invention utilizes the carbon monoxide in charing furnace gas and hydrogen to prepare natural gas liquids, and utilizes nitrogen coproduction liquefied ammonia wherein, and the useful component that enterprise can be made to carbonize in furnace gas obtains Appropriate application.
Description
Technical field
The invention belongs to Sweet natural gas production technical field, be specifically related to a kind of processing method carbonizing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas.
Background technology
Charing furnace gas be utilize high-quality jurassic period non-caking coal and weakly caking coal to be raw material, in charring furnace by destructive distillation produce produce in blue charcoal process be rich in hydrocarbon gas.When utilizing charring furnace destructive distillation to produce blue charcoal, often produce outside 1 ton of blue charcoal removing charring furnace reuse and blue charcoal drying, can 400-500Nm be obtained
3charring furnace gas, this gas heating value is 7500kJ/Nm
3.End the whole nation in 2013 and produce blue charcoal about 7,000 ten thousand tons altogether, wherein 4,000 ten thousand tons, Shaanxi, 2,000 ten thousand tons, Xinjiang, the Inner Mongol and 1,000 ten thousand tons, Ningxia, charing furnace gas can supply 280-350 hundred million Nm outward
3.Current enterprise is abundant not for the utilization of charing furnace gas, not only works the mischief to environment, has run counter to the relevant policies that national energy-saving reduces discharging, have impact on the development of whole industry simultaneously.
In charing furnace gas, each component content scope is as following table:
Simultaneously also containing impurity such as coal tar, dust granules, sulfide and moisture in this gas.Its medium sulphide content comprises hydrogen sulfide, sulfurous gas, sulphur carbonoxide, thiomethyl alcohol, thiophene etc.
Utilize Jin You small part enterprise by approach such as scoria lime stone, smelting magnesium and generatings at present for charing furnace gas, most of enterprise does not recycle, and there is the problems such as and environmental pollution low to charing furnace gas utilization ratio.From charing composition of fumes, contain more valuable, available composition in this gas as N
2, CO, H
2, by producing the processing method of natural gas liquids coproduction liquefied ammonia to charing furnace gas, being not only conducive to environment protection, improving energy-saving and emission-reduction, simultaneously can enterprise added value of product, bring considerable benefit.
Summary of the invention
The object of this invention is to provide a kind of processing method carbonizing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas, effectively can solve enterprise's technical problem low to charing furnace gas utilization ratio by this processing method, improve the value added of product.
The technical solution adopted in the present invention is:
The processing method of charing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas, is characterized in that:
Realized by following steps:
Step one: filter:
Furnace gas will be carbonized by strainer, the non-pneumatic impurity in removing gas, rough purification charing furnace gas;
Step 2: compression:
Adopt reciprocation compressor or radial compressor, charring furnace air pressure is reduced to 0.01-5.0Mpa;
Step 3: deoxidation:
Utilize dehydrogenation catalyst, it is 0.5% that the amount of oxygen in charing furnace gas is reduced to volume fraction;
Step 4: nitrogen separation:
Adopt vacuum pressure varying adsorption technology to isolate the nitrogen carbonized in furnace gas, making the nitrogen amount carbonized in furnace gas be reduced to volume fraction is 1%;
Step 5: wide temperature sulfur-resisting transformation:
Add water vapour, adopt wide temperature sulfur resistant conversion process, the hydrogen in adjustment charing furnace gas and the volume ratio of carbon monoxide are (3.2-3.5): 1, make the organosulfur carbonized in furnace gas be transformed into hydrogen sulfide simultaneously;
Step 6: desulfurization and decarburization:
Adopt the method for N methyldiethanol amine, Polyethylene glycol dimethyl ether or methanol wash column, make the sour gas scale of construction in charing furnace gas be down to 0.1ppm, it is 0.3% that carbonic acid gas is down to volume fraction;
Step 7: methanation:
Utilize nickel-base catalyst, adopt multistage methanation reaction, obtain the gaseous mixture based on methane, methane synthesis employing is multistage passes through methanation process or band circulation adiabatic methanation process without circulation primary, control methanation reaction temperature is 250-700 DEG C, pressure is 1-10Mpa, reaction heat for the production of steam, for step 5;
Step 8: be separated:
Moisture in the gaseous mixture using molecular sieve to remove based on methane and carbonic acid gas, amount of moisture is down to lppm, and amount of carbon dioxide is down to 50ppm;
Step 9: liquefaction:
Adopt azeotrope cryogenic liquefying technology to obtain the methane being greater than 99.5% purity, send into liquefying plant after re-heat and liquefy;
Step 10: liquefied ammonia synthesizes:
Inputting hydrogen in step 4 gained nitrogen, is compressedly pressurized to 20-30Mpa, in ammonia synthesis converter, catalyze and synthesize ammonia, and through water-cooled, ammonia is cold is cooled to-15 DEG C, and isolate liquefied ammonia wherein, unreacted gas returns ammonia synthesis converter cyclic production.
In step one, load coke or gac in strainer, filter outlet installs wire cloth, and separated space is left in bottom, and air-flow is outflow filter from bottom to top.
In step 3, dehydrogenation catalyst is selected from Fe/Al
2o
3, Fe-Mo/Al
2o
3, Co-Mo/Al
2o
3.
In step 7, nickel-base catalyst is selected from Ni/Al
2o
3, Ni/Al
2o
3-MgO.
The present invention has the following advantages:
By a kind of processing method carbonizing furnace gas preparing liquefied natural gas coproduction liquefied ammonia provided by the invention, the useful component that enterprise can be made to carbonize in furnace gas obtains Appropriate application, carbon monoxide and hydrogen form natural gas liquids by methanation synthesis, and nitrogen is produced for the synthesis of ammonia.Effectively can slow down the situation of China's many ground natural gas supply deficiency after enforcement, improve enterprise to charing furnace gas utilization ratio simultaneously, realize energy-saving and emission-reduction, enrich product industrial chain, improve enterprise product added value, increase business economic, realize enterprise clean production.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
The processing method of charing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas involved in the present invention, what utilize is for raw material with China's Factory, Shenmu, Shanxi, Fugu and regional high-quality jurassic period non-caking coal such as Changji, Hami and the Inner Mongol, Ningxia etc. and weakly caking coal, in charring furnace by destructive distillation produce produce in blue charcoal process be rich in hydrocarbon charing furnace gas, generally production technique implement before need to raw material charing furnace gas carry out Components identification.In charing furnace gas, each component content scope is as following table:
Simultaneously also containing impurity such as coal tar, dust granules, sulfide and moisture in this gas.Its medium sulphide content comprises hydrogen sulfide, sulfurous gas, sulphur carbonoxide, thiomethyl alcohol, thiophene etc.
Specifically realized by following steps:
Step one: filter:
Furnace gas will be carbonized by strainer, the non-pneumatic impurity in removing gas, rough purification charing furnace gas;
Load coke or gac in strainer, filter outlet installs wire cloth, and separated space is left in bottom, and air-flow is outflow filter from bottom to top.
Step 2: compression:
Adopt reciprocation compressor or radial compressor, charring furnace air pressure is reduced to 0.01-5.0Mpa.
Step 3: deoxidation:
Dehydrogenation catalyst is utilized (to be selected from Fe/Al
2o
3, Fe-Mo/Al
2o
3, Co-Mo/Al
2o
3, all with Al
2o
3for carrier), it is 0.5% that the amount of oxygen in charing furnace gas is reduced to volume fraction.
Step 4: nitrogen separation:
Adopt vacuum pressure varying adsorption technology to isolate the nitrogen carbonized in furnace gas, making the nitrogen amount carbonized in furnace gas be reduced to volume fraction is 1%.
Step 5: wide temperature sulfur-resisting transformation:
Add water vapour, adopt wide temperature sulfur resistant conversion process, the hydrogen in adjustment charing furnace gas and the volume ratio of carbon monoxide are (3.2-3.5): 1, make the organosulfur carbonized in furnace gas be transformed into hydrogen sulfide simultaneously.
Step 6: desulfurization and decarburization:
Adopt the method for N methyldiethanol amine, Polyethylene glycol dimethyl ether or methanol wash column, make the sour gas scale of construction in charing furnace gas be down to 0.1ppm, it is 0.3% that carbonic acid gas is down to volume fraction.
Step 7: methanation:
Nickel-base catalyst is utilized (to be selected from Ni/Al
2o
3, Ni/Al
2o
3-MgO, the former is with Al
2o
3for carrier, the latter is with Al
2o
3-MgO is carrier), adopt multistage methanation reaction, obtain the gaseous mixture based on methane, methane synthesis employing is multistage passes through methanation process or band circulation adiabatic methanation process without circulation primary, control methanation reaction temperature is 250-700 DEG C, pressure is 1-10Mpa, reaction heat for the production of steam, for step 5.
Step 8: be separated:
Moisture in the gaseous mixture using molecular sieve to remove based on methane and carbonic acid gas, amount of moisture is down to lppm, and amount of carbon dioxide is down to 50ppm.
Step 9: liquefaction:
Adopt azeotrope cryogenic liquefying technology to obtain the methane being greater than 99.5% purity, send into liquefying plant after re-heat and liquefy.
Step 10: liquefied ammonia synthesizes:
Inputting hydrogen in step 4 gained nitrogen, is compressedly pressurized to 20-30Mpa, in ammonia synthesis converter, catalyze and synthesize ammonia, and through water-cooled, ammonia is cold is cooled to-15 DEG C, and isolate liquefied ammonia wherein, unreacted gas returns ammonia synthesis converter cyclic production.
Embodiment 1:
The raw material charing furnace gas of the present embodiment mainly forms and specifically sees the following form: (tolerance 40000Nm
3/ h, temperature 40 DEG C)
Simultaneously also containing impurity such as coal tar, dust granules, sulfide and moisture in gas.Its medium sulphide content comprises hydrogen sulfide, sulfurous gas, sulphur carbonoxide, thiomethyl alcohol, thiophene etc.
Step one: filter:
Furnace gas will be carbonized by strainer, the non-pneumatic impurity in removing gas, rough purification charing furnace gas;
Load coke in strainer, filter outlet installs wire cloth, and separated space is left in bottom, and air-flow is outflow filter from bottom to top.
Step 2: compression:
Adopt reciprocation compressor, charring furnace air pressure is reduced to 0.01Mpa.
Step 3: deoxidation:
Utilize dehydrogenation catalyst (Fe/Al
2o
3, with Al
2o
3for carrier), it is 0.5% that the amount of oxygen in charing furnace gas is reduced to volume fraction.
Step 4: nitrogen separation:
Adopt vacuum pressure varying adsorption technology to isolate the nitrogen carbonized in furnace gas, making the nitrogen amount carbonized in furnace gas be reduced to volume fraction is 1%.
Step 5: wide temperature sulfur-resisting transformation:
Add water vapour, adopt wide temperature sulfur resistant conversion process, the hydrogen in adjustment charing furnace gas and the volume ratio of carbon monoxide are 3.2:1, make the organosulfur carbonized in furnace gas be transformed into hydrogen sulfide simultaneously.
Step 6: desulfurization and decarburization:
Adopt the method that N methyldiethanol amine is washed, make the sour gas scale of construction in charing furnace gas be down to 0.1ppm, it is 0.3% that carbonic acid gas is down to volume fraction.
Step 7: methanation:
Utilize nickel-base catalyst (Ni/Al
2o
3, with Al
2o
3for carrier), adopt multistage methanation reaction, obtain the gaseous mixture based on methane, methane synthesis employing is multistage passes through methanation process without circulation primary, control that methanation reaction temperature is 250 DEG C, pressure is 1Mpa, reaction heat for the production of steam, for step 5.
Step 8: be separated:
Moisture in the gaseous mixture using molecular sieve to remove based on methane and carbonic acid gas, amount of moisture is down to lppm, and amount of carbon dioxide is down to 50ppm.
Step 9: liquefaction:
Adopt azeotrope cryogenic liquefying technology to obtain the methane being greater than 99.5% purity, send into liquefying plant after re-heat and liquefy.Natural gas liquids 5.854 tons/h can be obtained.
Step 10: liquefied ammonia synthesizes:
Inputting hydrogen in step 4 gained nitrogen, is compressedly pressurized to 20Mpa, in ammonia synthesis converter, catalyze and synthesize ammonia, and through water-cooled, ammonia is cold is cooled to-15 DEG C, and isolate liquefied ammonia wherein, unreacted gas returns ammonia synthesis converter cyclic production.Liquefied ammonia 25.728 tons/h can be produced.
Embodiment 2:
The raw material charing furnace gas of the present embodiment mainly forms and specifically sees the following form: (tolerance 40000Nm
3/ h, temperature 40 DEG C)
Simultaneously also containing impurity such as coal tar, dust granules, sulfide and moisture in gas.Its medium sulphide content comprises hydrogen sulfide, sulfurous gas, sulphur carbonoxide, thiomethyl alcohol, thiophene etc.
Step one: filter:
Furnace gas will be carbonized by strainer, the non-pneumatic impurity in removing gas, rough purification charing furnace gas;
Load coke in strainer, filter outlet installs wire cloth, and separated space is left in bottom, and air-flow is outflow filter from bottom to top.
Step 2: compression:
Adopt reciprocation compressor, charring furnace air pressure is reduced to 2.5Mpa.
Step 3: deoxidation:
Utilize dehydrogenation catalyst (Fe-Mo/Al
2o
3, with Al
2o
3for carrier), it is 0.5% that the amount of oxygen in charing furnace gas is reduced to volume fraction.
Step 4: nitrogen separation:
Adopt vacuum pressure varying adsorption technology to isolate the nitrogen carbonized in furnace gas, making the nitrogen amount carbonized in furnace gas be reduced to volume fraction is 1%.
Step 5: wide temperature sulfur-resisting transformation:
Add water vapour, adopt wide temperature sulfur resistant conversion process, the hydrogen in adjustment charing furnace gas and the volume ratio of carbon monoxide are 3.3:1, make the organosulfur carbonized in furnace gas be transformed into hydrogen sulfide simultaneously.
Step 6: desulfurization and decarburization:
Adopt the method that Polyethylene glycol dimethyl ether is washed, make the sour gas scale of construction in charing furnace gas be down to 0.1ppm, it is 0.3% that carbonic acid gas is down to volume fraction.
Step 7: methanation:
Utilize nickel-base catalyst (Ni/Al
2o
3, with Al
2o
3for carrier), adopt multistage methanation reaction, obtain the gaseous mixture based on methane, methane synthesis employing is multistage passes through methanation process without circulation primary, control that methanation reaction temperature is 500 DEG C, pressure is 5Mpa, reaction heat for the production of steam, for step 5.
Step 8: be separated:
Moisture in the gaseous mixture using molecular sieve to remove based on methane and carbonic acid gas, amount of moisture is down to lppm, and amount of carbon dioxide is down to 50ppm.
Step 9: liquefaction:
Adopt azeotrope cryogenic liquefying technology to obtain the methane being greater than 99.5% purity, send into liquefying plant after re-heat and liquefy.Natural gas liquids 7.29 tons/h can be obtained.
Step 10: liquefied ammonia synthesizes:
Inputting hydrogen in step 4 gained nitrogen, is compressedly pressurized to 25Mpa, in ammonia synthesis converter, catalyze and synthesize ammonia, and through water-cooled, ammonia is cold is cooled to-15 DEG C, and isolate liquefied ammonia wherein, unreacted gas returns ammonia synthesis converter cyclic production.Liquefied ammonia 12.328 tons/h can be produced.
Embodiment 3:
The raw material charing furnace gas of the present embodiment mainly forms and specifically sees the following form: (tolerance 40000Nm
3/ h, temperature 40 DEG C)
Simultaneously also containing impurity such as coal tar, dust granules, sulfide and moisture in gas.Its medium sulphide content comprises hydrogen sulfide, sulfurous gas, sulphur carbonoxide, thiomethyl alcohol, thiophene etc.
Step one: filter:
Furnace gas will be carbonized by strainer, the non-pneumatic impurity in removing gas, rough purification charing furnace gas;
Load gac in strainer, filter outlet installs wire cloth, and separated space is left in bottom, and air-flow is outflow filter from bottom to top.
Step 2: compression:
Adopt radial compressor, charring furnace air pressure is reduced to 5.0Mpa.
Step 3: deoxidation:
Utilize dehydrogenation catalyst (Co-Mo/Al
2o
3, with Al
2o
3for carrier), it is 0.5% that the amount of oxygen in charing furnace gas is reduced to volume fraction.
Step 4: nitrogen separation:
Adopt vacuum pressure varying adsorption technology to isolate the nitrogen carbonized in furnace gas, making the nitrogen amount carbonized in furnace gas be reduced to volume fraction is 1%.
Step 5: wide temperature sulfur-resisting transformation:
Add water vapour, adopt wide temperature sulfur resistant conversion process, the hydrogen in adjustment charing furnace gas and the volume ratio of carbon monoxide are 3.5:1, make the organosulfur carbonized in furnace gas be transformed into hydrogen sulfide simultaneously.
Step 6: desulfurization and decarburization:
Adopt the method for methanol wash column, make the sour gas scale of construction in charing furnace gas be down to 0.1ppm, it is 0.3% that carbonic acid gas is down to volume fraction.
Step 7: methanation:
Utilize nickel-base catalyst (Ni/Al
2o
3-MgO, with Al
2o
3-MgO is carrier), adopt multistage methanation reaction, obtain the gaseous mixture based on methane, methane synthesis adopts band circulation adiabatic methanation process, control that methanation reaction temperature is 700 DEG C, pressure is 10Mpa, reaction heat for the production of steam, for step 5.
Step 8: be separated:
Moisture in the gaseous mixture using molecular sieve to remove based on methane and carbonic acid gas, amount of moisture is down to lppm, and amount of carbon dioxide is down to 50ppm.
Step 9: liquefaction:
Adopt azeotrope cryogenic liquefying technology to obtain the methane being greater than 99.5% purity, send into liquefying plant after re-heat and liquefy.Natural gas liquids 3.268 tons/h can be obtained.
Step 10: liquefied ammonia synthesizes:
Inputting hydrogen in step 4 gained nitrogen, is compressedly pressurized to 30Mpa, in ammonia synthesis converter, catalyze and synthesize ammonia, and through water-cooled, ammonia is cold is cooled to-15 DEG C, and isolate liquefied ammonia wherein, unreacted gas returns ammonia synthesis converter cyclic production.Liquefied ammonia 18.76 tons/h can be produced.
Content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (1)
1. carbonize the processing method of furnace gas liquefied ammonia co-production of liquefied Sweet natural gas, it is characterized in that:
Realized by following steps:
Step one: filter:
Furnace gas will be carbonized by strainer, the non-pneumatic impurity in removing gas, rough purification charing furnace gas;
Load gac in strainer, filter outlet installs wire cloth, and separated space is left in bottom, and air-flow is outflow filter from bottom to top;
Step 2: compression:
Adopt radial compressor, charring furnace air pressure is reduced to 5.0MPa;
Step 3: deoxidation:
Utilize dehydrogenation catalyst, it is 0.5% that the amount of oxygen in charing furnace gas is reduced to volume fraction;
Described dehydrogenation catalyst is Co-Mo/Al
2o
3, with Al
2o
3for carrier;
Step 4: nitrogen separation:
Adopt vacuum pressure varying adsorption technology to isolate the nitrogen carbonized in furnace gas, making the nitrogen amount carbonized in furnace gas be reduced to volume fraction is 1%;
Step 5: wide temperature sulfur-resisting transformation:
Add water vapour, adopt wide temperature sulfur resistant conversion process, the hydrogen in adjustment charing furnace gas and the volume ratio of carbon monoxide are 3.5:1, make the organosulfur carbonized in furnace gas be transformed into hydrogen sulfide simultaneously;
Step 6: desulfurization and decarburization:
Adopt the method for methanol wash column, make the sour gas scale of construction in charing furnace gas be down to 0.1ppm, it is 0.3% that carbonic acid gas is down to volume fraction;
Step 7: methanation:
Utilize nickel-base catalyst, adopt multistage methanation reaction, obtain the gaseous mixture based on methane, methane synthesis adopts band circulation adiabatic methanation process, control that methanation reaction temperature is 700 DEG C, pressure is 10MPa, reaction heat for the production of steam, for step 5;
Described nickel-base catalyst is Ni/Al
2o
3-MgO, with Al
2o
3-MgO is carrier;
Step 8: be separated:
Moisture in the gaseous mixture using molecular sieve to remove based on methane and carbonic acid gas, amount of moisture is down to lppm, and amount of carbon dioxide is down to 50ppm;
Step 9: liquefaction:
Adopt azeotrope cryogenic liquefying technology to obtain the methane being greater than 99.5% purity, send into liquefying plant after re-heat and liquefy;
Step 10: liquefied ammonia synthesizes:
Inputting hydrogen in step 4 gained nitrogen, is compressedly pressurized to 30MPa, in ammonia synthesis converter, catalyze and synthesize ammonia, and through water-cooled, ammonia is cold is cooled to-15 DEG C, and isolate liquefied ammonia wherein, unreacted gas returns ammonia synthesis converter cyclic production.
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| CN109280570A (en) * | 2018-10-22 | 2019-01-29 | 孙洁 | Gas-tight ring circulation comprehensive utilizes the technique for preparing natural gas after synthetic ammonia tower |
| CN111100717A (en) * | 2018-10-26 | 2020-05-05 | 苏州盖沃净化科技有限公司 | Method and device for preparing natural gas from coal gas |
| CN113769710A (en) * | 2021-10-12 | 2021-12-10 | 宁夏天雄碳材料有限公司 | Active carbon preparation combustible gas cyclic utilization device |
| CN114409503B (en) * | 2021-11-23 | 2024-06-11 | 中国平煤神马控股集团有限公司 | Process for preparing BDO and co-producing liquid ammonia by using coke oven gas |
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