CN103074133A - Processing method for outward-exhausting coal gas in internal heating-type coal carbonization process - Google Patents
Processing method for outward-exhausting coal gas in internal heating-type coal carbonization process Download PDFInfo
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- CN103074133A CN103074133A CN2012105980134A CN201210598013A CN103074133A CN 103074133 A CN103074133 A CN 103074133A CN 2012105980134 A CN2012105980134 A CN 2012105980134A CN 201210598013 A CN201210598013 A CN 201210598013A CN 103074133 A CN103074133 A CN 103074133A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a processing method for outward-exhausting coal gas in an internal heating-type coal carbonization process, which is based on a coal carbonization technology (application number 201110058345.9) taking CO2 as a temperature-controlled component in the combustion process. The used oxidation agent in the coal carbonization process is a mixture of enriched oxygen and CO2 gas, the outward-exhausting coal gas is mainly composed of H2, CO, CH4, CO2 and H2O, the coal gas becomes first decarbonization gas TT1Q through a CO2 desorption process, the first decarbonization gas TT1Q is used for cogenerating H2 and LNG, and H2 is used in a coal tar hydrogenation process, so that a combined technology of internal heating-type semi coke preparation, coal tar hydrogenation and H2 and LNG preparation by coal gas is formed. As the process for producing LNG is the process for purifying H2 simultaneously, the process has high economical efficiency, and is particularly suitable for the combined process of semi coke preparation by internal heating-type carbonization, coal tar hydrogenation and cogeneration of H2 and LNG by coal gas.
Description
Technical field
The present invention relates to a kind of internally heated coal carbonization process and efflux the coal gas working method, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is oxygen rich air and CO
2The mixture of gas effluxes coal gas mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O, this coal gas is through taking off CO
2Process becomes the first decarbonization gas TT1Q, uses the first decarbonization gas TT1Q coproduction H
2And LNG, H
2For the coal tar hydrogenating process, thereby consist of the blue charcoal of internal heat type system, hydrogenation of tar, coal gas H processed
2With the LNG combination process.Because producing the process of LNG is exactly the H that purifies simultaneously
2Process, this process possess the height economy.
Background technology
Produce at present the internally heated coal carbonization process of coal tar such as the blue charcoal process of internal heat type coal system, if according to the blue charcoal of internal heat type destructive distillation system, self-produced hydrogenation of tar, gas production H
2Form combination process, usually have excessive coal gas.Because blue charcoal stove uses air to be oxygenant usually, contains a large amount of N in the superfluous coal gas
2, based on PSA technology and cold separation technology, reclaim CH in the superfluous coal gas
4Existing various processing schemes all uneconomical, therefore usually this gas is made gas turbine powered generator fuel or gas fired-boiler fuel, compare with coal producing steam or coal power generation, form in essence " gas change coal ", its irrationality is apparent.
" a kind of with CO based on the patent application that the inventor proposes
2Coal carbonization technique (application number 201110058345.9) for temperature control component in combustion ", the blue charcoal process of internal heat type coal system effluxes the N in the coal gas
2Partly or entirely by CO
2Displacement effluxes coal gas mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O, this coal gas is through taking off CO
2Process becomes the first decarbonization gas TT1Q, uses the first decarbonization gas TT1Q coproduction H
2And LNG, H
2For the coal tar hydrogenating process, can realize the complete utilization to active principle in the coal gas.The present invention with utilize blue charcoal coal gas that independent H processed is set respectively
2Process and independent CH processed
4Process is compared, and is exactly the H that purifies simultaneously owing to producing the process of LNG
2Process, thereby energy consumption is reduced investment outlay, saved to the flow process Simplification, therefore possess the height economy.The method of the invention has no report.
Therefore, the object of the invention is to propose a kind of internally heated coal carbonization process and efflux the coal gas working method, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is oxygen rich air (or purity oxygen) and CO
2The mixture of gas effluxes coal gas mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O, this coal gas is through taking off CO
2Process becomes the first decarbonization gas TT1Q, uses the first decarbonization gas TT1Q coproduction H
2And LNG, H
2For the coal tar hydrogenating process, thereby consist of the blue charcoal of internal heat type system, hydrogenation of tar, coal gas H processed
2With the LNG combination process.
Summary of the invention
A kind of internally heated coal carbonization process of the present invention effluxes the coal gas working method, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is oxygen rich air and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O is characterized in that comprising following steps:
1. at the first decarbonization process, the dry distillation of coal is effluxed coal gas F000 use at least a portion CO among the unstripped gas F100 as the first decarbonization process unstripped gas F100
2Be removed and obtain the first decarbonization gas TT1Q;
2. at shift conversion step, the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ, becomes " the second decarbonization process " unstripped gas F200 after the conversion gas BHQ cooled dehydrated; Amounts of hydrogen among the conversion gas BHQ: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, " the second decarbonization process " unstripped gas F200 removes hydrogen sulfide, CO at this
2Obtain the second decarbonization gas TT2Q;
4. in the methanation operation, remove that sulphur obtains fine gas JZQ among the second decarbonization gas TT2Q, fine gas JZQ enters the methanation reaction process, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ;
5. in the liquefaction operation, methanation obtains the CH that liquefies through the subcooling process after generating gas SCQ dehydration
4With gas hydrogen.
Feature of the present invention further is, the dry distillation of coal effluxes coal gas F000 and enters " the first decarbonization process " and become thick desulfurization coal gas CTLQ through wet desulphurization hydrogen operation before, and thick desulfurization coal gas CTLQ makes " the first decarbonization process " unstripped gas F100 and uses.
Feature of the present invention further is, the dry distillation of coal effluxes coal gas F000 and enters " the first decarbonization process " and pass through before wet desulphurization hydrogen operation, thick desulfurization coal gas CTLQ becomes thick purified gas CJHQ through PSA or TSA detar operation, and thick purified gas CJHQ makes " the first decarbonization process " unstripped gas F100 and uses.
Feature of the present invention further is, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is purity oxygen and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O:
1. at the first decarbonization process, adopt low pressure VPSA decarbonization process with at least a portion CO among the first decarbonization process unstripped gas F100
2Remove and obtain the first decarbonization gas TT1Q;
2. at shift conversion step, adopt the sulphur resisting and low temp conversing technology, be that 160～360 ℃, pressure are that the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ under 0.6～10.0MPa (absolute pressure) condition in temperature; Amounts of hydrogen among the conversion gas BHQ: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, adopt selectivity to take off H
2S, CO
2Technology makes " the second decarbonization process " unstripped gas F200 finish hydrogen sulfide, CO at this
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, remove that sulphur is down to≤0.1mg/Nm its total sulfur content among the second decarbonization gas TT2Q
3Obtain fine gas JZQ; Fine gas JZQ enters the methanation reaction process, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ;
5. in the liquefaction operation, methanation obtains the CH that liquefies through the subcooling process after generating gas SCQ dehydration
4With gas hydrogen.
Feature of the present invention further is, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is purity oxygen and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O:
1. at the first decarbonization process, adopt the VPSA decarbonization process with CO among the unstripped gas F100
2Be removed to≤5 volume % obtain the first decarbonization gas TT1Q, and process operation pressure is lower than 0.3MPa (absolute pressure);
2. at shift conversion step, adopt the sulphur resisting and low temp conversing technology, be that 160～360 ℃, pressure are that the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ under 0.8～5.0MPa (absolute pressure) condition in temperature; Amounts of hydrogen among the unstripped gas F200: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, adopting the organic amine aqueous solution is solvent removal hydrogen sulfide and CO
2, make " the second decarbonization process " unstripped gas F200 finish hydrogen sulfide, CO at this
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, adopt the zinc oxide desulfurization technology to remove that sulphur obtains fine gas JZQ among the second decarbonization gas TT2Q, fine gas JZQ total sulfur content≤0.1mg/Nm
3Fine gas JZQ enters the methanation reaction process, is under 0.8～5.0MPa (absolute pressure) condition at pressure, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ; The CO transformation efficiency is greater than 98 volume %, CO
2Transformation efficiency is greater than 95 volume %.
5. in the liquefaction operation, after methanation generates gas SCQ dehydration, be to obtain LNG and gas hydrogen PH2, the H of gas hydrogen PH2 through the subcooling process under 0.8～5.0MPa (absolute pressure) condition at pressure
2Purity is greater than 95 volume %.
Feature of the present invention further is, preferred working pressure is:
1. at the first decarbonization process, working pressure is lower than 0.2MPa (absolute pressure);
2. at shift conversion step, working pressure is 0.8～2.0MPa (absolute pressure);
3. at the second decarbonization process, working pressure is 0.8～2.0MPa (absolute pressure), and to adopt Aqueous Activated MethyldiethanolamineSolutions Solutions be the solvent depriving hydrogen sulphide, take off CO
2
4. in the methanation operation, working pressure is 0.8～2.0MPa (absolute pressure);
5. in the liquefaction operation, working pressure is 2.5～5.0MPa (absolute pressure).
In order to transform as far as possible CO and CO
2, feature of the present invention further is:
4. in the methanation operation, the CO transformation efficiency is greater than 99 volume %, CO
2Transformation efficiency is greater than 98 volume %;
5. in the liquefaction operation, methanation obtains LNG and gas hydrogen PH2, the H of gas hydrogen PH2 through the subcooling process after generating gas SCQ dehydration
2Purity is greater than 98 volume %.
Feature of the present invention further is to arrange the hydrogen purification operation: 6. in the hydrogen purification operation, adopt the PSA technology, gas hydrogen PH2 is separated into pure hydrogen CH2 and stripping gas, the H of pure hydrogen CH2
2Purity is greater than 99 volume %.
Embodiment
Below describe the present invention in detail.
Pressure of the present invention refers to absolute pressure.
Concentration of component of the present invention when not specializing, is volumetric concentration.
The technical scheme that the present invention uses relates to wet desulphurization hydrogen, PSA or TSA detar, shortening detoxification (comprising that deoxidation gas, organosulfur are converted into inorganic sulfur etc.), carbon monoxide under low temperature sulfur-resisting transformation, carbonylsulfide medium temperature hydrolyzation, PSA or TSA decarbonation, PSA or VPSA divided gas flow, methanation, the low temperature separation process of blue charcoal coal gas etc., these technology are known technology, wherein most of technology existing description in the inventor's following patent application, this paper no longer too much describes.
Table 1 is loaded with the patent application of Description of Related Art
| Date of application | Application number | Denomination of invention |
| 2011-03-05 | 201110058345.9 | A kind of with CO 2Coal carbonization technique for temperature control component in combustion |
| 2011-06-17 | 201110172569.2 | A kind of internally heated coal carbonization multi-production process of coproduction high methane gas |
| 2011-07-18 | 201110221627.6 | A kind of usefulness contains H 2、N 2Polycomponent gas prepares the method for specific composition hydrogen and nitrogen gas |
A kind of internally heated coal carbonization process of the present invention effluxes the coal gas working method, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is the mixture of oxygen rich air and CO2 gas, and the dry distillation of coal effluxes coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O is characterized in that comprising following steps:
1. at the first decarbonization process, the dry distillation of coal is effluxed coal gas F000 use at least a portion CO among the unstripped gas F100 as the first decarbonization process unstripped gas F100
2Be removed and obtain the first decarbonization gas TT1Q;
2. at shift conversion step, the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ, becomes " the second decarbonization process " unstripped gas F200 after the conversion gas BHQ cooled dehydrated; Amounts of hydrogen among the conversion gas BHQ: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, " the second decarbonization process " unstripped gas F200 removes hydrogen sulfide, CO at this
2Obtain the second decarbonization gas TT2Q;
4. in the methanation operation, remove that sulphur obtains fine gas JZQ among the second decarbonization gas TT2Q, fine gas JZQ enters the methanation reaction process, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ;
5. in the liquefaction operation, methanation obtains the CH that liquefies through the subcooling process after generating gas SCQ dehydration
4With gas hydrogen.
Feature of the present invention further is, the dry distillation of coal effluxes coal gas F000 and enters " the first decarbonization process " and become thick desulfurization coal gas CTLQ through wet desulphurization hydrogen operation before, and thick desulfurization coal gas CTLQ makes " the first decarbonization process " unstripped gas F100 and uses.
Feature of the present invention further is, the dry distillation of coal effluxes coal gas F000 and enters " the first decarbonization process " and pass through before wet desulphurization hydrogen operation, thick desulfurization coal gas CTLQ becomes thick purified gas CJHQ through PSA or TSA detar operation, and thick purified gas CJHQ makes " the first decarbonization process " unstripped gas F100 and uses.
Feature of the present invention further is, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is purity oxygen and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O:
1. at the first decarbonization process, adopt low pressure VPSA decarbonization process with at least a portion CO among the first decarbonization process unstripped gas F100
2Remove and obtain the first decarbonization gas TT1Q;
2. at shift conversion step, adopt the sulphur resisting and low temp conversing technology, be that 160～360 ℃, pressure are that the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ under 0.6～10.0MPa (absolute pressure) condition in temperature; Amounts of hydrogen among the conversion gas BHQ: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, adopt selectivity to take off H
2S, CO
2Technology makes " the second decarbonization process " unstripped gas F200 finish hydrogen sulfide, CO at this
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, remove that sulphur is down to≤0.1mg/Nm its total sulfur content among the second decarbonization gas TT2Q
3Obtain fine gas JZQ; Fine gas JZQ enters the methanation reaction process, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ;
5. in the liquefaction operation, methanation obtains the CH that liquefies through the subcooling process after generating gas SCQ dehydration
4With gas hydrogen.
Feature of the present invention further is, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is purity oxygen and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O:
1. at the first decarbonization process, adopt the VPSA decarbonization process with CO among the unstripped gas F100
2Be removed to≤5 volume % obtain the first decarbonization gas TT1Q, and process operation pressure is lower than 0.3MPa (absolute pressure);
2. at shift conversion step, adopt the sulphur resisting and low temp conversing technology, be that 160～360 ℃, pressure are that the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ under 0.8～5.0MPa (absolute pressure) condition in temperature; Amounts of hydrogen among the unstripped gas F200: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, adopting the organic amine aqueous solution is solvent removal hydrogen sulfide and CO
2, make " the second decarbonization process " unstripped gas F200 finish hydrogen sulfide, CO at this
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, adopt the zinc oxide desulfurization technology to remove that sulphur obtains fine gas JZQ among the second decarbonization gas TT2Q, fine gas JZQ total sulfur content≤0.1mg/Nm
3Fine gas JZQ enters the methanation reaction process, is under 0.8～5.0MPa (absolute pressure) condition at pressure, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ; The CO transformation efficiency is greater than 98 volume %, CO
2Transformation efficiency is greater than 95 volume %.
5. in the liquefaction operation, after methanation generates gas SCQ dehydration, be to obtain LNG and gas hydrogen PH2, the H of gas hydrogen PH2 through the subcooling process under 0.8～5.0MPa (absolute pressure) condition at pressure
2Purity is greater than 95 volume %.
Feature of the present invention further is, preferred working pressure is:
1. at the first decarbonization process, working pressure is lower than 0.2MPa (absolute pressure);
2. at shift conversion step, working pressure is 0.8～2.0MPa (absolute pressure);
3. at the second decarbonization process, working pressure is 0.8～2.0MPa (absolute pressure), and to adopt Aqueous Activated MethyldiethanolamineSolutions Solutions be the solvent depriving hydrogen sulphide, take off CO
2
4. in the methanation operation, working pressure is 0.8～2.0MPa (absolute pressure);
5. in the liquefaction operation, working pressure is 2.5～5.0MPa (absolute pressure).
In order to transform as far as possible CO and CO
2, feature of the present invention further is:
4. in the methanation operation, the CO transformation efficiency is greater than 99 volume %, CO
2Transformation efficiency is greater than 98 volume %;
5. in the liquefaction operation, methanation obtains LNG and gas hydrogen PH2, the H of gas hydrogen PH2 through the subcooling process after generating gas SCQ dehydration
2Purity is greater than 98 volume %.
Feature of the present invention further is to arrange the hydrogen purification operation: 6. in the hydrogen purification operation, adopt the PSA technology, gas hydrogen PH2 is separated into pure hydrogen CH2 and stripping gas, the H of pure hydrogen CH2
2Purity is greater than 99 volume %.
Embodiment
The blue charcoal devices of certain 1,350 ten thousand ton/years of long-flame coal system, produce about 950,000 marks cube/time efflux coal gas, its supporting 1,600,000 ton/years of coal tar hydrogenating conversion systems need hydrogen approximately 120,000 marks cube/time, process coal gas coproduction H according to the present invention
2And LNG.
Blue charcoal device goes out blue charcoal producer gas, through directly removing most of tar and water after washing, the water-cooled, coal gas further indirectly cools off through recirculated water and reduces temperature to 40～50 ℃ after the washing, between finish after cold and take off liquid coal gas after cold between obtaining after the gas-liquid separation, between take off liquid coal gas after cold compression boosted through blower fan after, become coal gas after the electric fishing through the electrical tar precipitator detar, coal gas is divided into two portions after the electric fishing, first part returns blue charcoal stove (making circulation heat-carrying gas and fuel gas), and second section effluxes coal gas F000 as the dry distillation of coal and uses.Pressure when the dry distillation of coal effluxes coal gas F000 and enters treating processes of the present invention is～5KPaG, composition of coal gas such as table 2.
Table 2 dry distillation of coal effluxes coal gas F000 and forms
| Sequence number | Form | Design load | Volumetric flow rate |
| ? | ? | Mole fraction (butt) | Standard cubic meter/time |
| 1 | H 2 | 30.73％ | ? |
| 2 | CO 2 | 49.31％ | ? |
| 3 | CO | 10.18％ | ? |
| 4 | O 2 | 0.20％ | ? |
| 5 | N 2 | ? | ? |
| 6 | CH 4 | 7.06％ | ? |
| 7 | C 2H 4 | ? | ? |
| 8 | C 2H 6 | 0.64％ | ? |
| 9 | H 2O | 1.88％ | ? |
| 10 | Add up to | 100.00％ | ? |
| Volumetric flow rate | Nm 3/H | ? | 950000 |
Table 3 dry distillation of coal effluxes coal gas F000 foreign matter content
| Sequence number | Form | Design load | Limits value |
| ? | ? | (butt) | (butt) |
| 1 | Tar | 106.1mg/Nm 3 | ≤150 |
| 2 | Naphthalene | 16.7mg/Nm 3 | ≤20 |
| 3 | H 2S (before the depriving hydrogen sulphide) | 1209mg/Nm 3 | ≤1500 |
| ? | H 2S (behind the depriving hydrogen sulphide) | 200mg/Nm 3 | ≤300 |
| 4 | Organosulfur | 500～700mg/Nm3 | ≤750 |
According to the present invention, the course of processing comprises following operation:
1. at the first decarbonization process, the dry distillation of coal effluxes coal gas F000, become thick desulfurization coal gas CTLQ through PDS aqueous solution wet desulphurization hydrogen process, pressure was～0.003MPa (gauge pressure) after thick desulfurization coal gas CTLQ cushioned through gas holder, boost to 80KPa (gauge pressure) by centrifugal blower, after the PSA detar, make " the first decarbonization process " unstripped gas F100 and use; Adopt low pressure VPSA decarbonization process with CO among the unstripped gas F100
2Be removed to≤5 volume %, since large-minded, three cover parallel arrangement adopted, the 6-3-1VPSA flow process; Adsorption operations pressure 50～60KPa (gauge pressure);
2. at shift conversion step, the compressed machine of the first decarbonization gas TT1Q boosts to 1.7MPa (absolute pressure) as the shift conversion step unstripped gas, through after the conditioning tower, be preheating to 180 ℃, through hydrogenation detoxification beds, carry out hydrogenation deoxidation gas, the hydrogenation olefin saturated, the organosulfur hydrocracking is the reactions such as inorganic sulfur, the detoxification reaction effluent reduces temperature to approximately 200 ℃, entering the sulphur tolerant CO shift beds carries out Partial Transformation reaction and obtains the transformationreation effluent, so that after the methanation total hydrogen amount be 12.2～12.7 ten thousand sides/hour, make the volume ratio of all the other hydrogen and carbon monoxide component near 3: 1; The transformationreation effluent carries out the carbonyl sulfide hydrolysis reaction through carbonylsulfide medium temperature hydrolyzation beds and obtains the hydrolysis reaction effluent; Finish after the hydrolysis reaction effluent is cooled to 40 ℃ gas, moisture from, dehydration gas is as the unstripped gas F200 of " the second decarbonization process "; In order to keep H in the conversion unstripped gas
2S concentration is greater than 150mg/Nm
3, in the conversion unstripped gas, add the addition of C S as required
2
3. at the second decarbonization process, adopt the MDEA aqueous solution of activation, with hydrogen sulfide, CO among the unstripped gas F200 of " the second decarbonization process "
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, the second decarbonization gas TT2Q is at first through comprising that the organosulfur hydrocracking is the desulfurizing and purifying process of the processes such as inorganic sulfur, carbonyl sulfide hydrolysis, zinc oxide absorption, obtains total content≤0.1mg/Nm
3The methanation unstripped gas, the methanation unstripped gas makes (CO+CO through the methanation reaction process
2) generate CH with hydrogen reaction
4, obtain the methanation reaction effluent, conduct liquefaction unstripped gas after the cooled dehydrated; In the methanation operation, the CO transformation efficiency is greater than 99 volume %, CO
2Transformation efficiency is greater than 98 volume %;
5. in the liquefaction operation, methanation generates gas SCQ and boosts to 3.6MPa (absolute pressure) after dehydration, adopts MRC subcooling technology that methanation is generated CH among the gas SCQ
4Liquefaction obtains LNG, and non-condensable gas is hydrogen product, the H of gas hydrogen PH2
2Purity is greater than 98 volume %.
The material balance table sees Table 4 to table 7.
Table 4 embodiment 1 material balance table 1
Table 5 embodiment 1 material balance table 2
Table 6 embodiment 1 material balance table 3
Table 7 embodiment 1 material balance table 4
Claims (8)
1. an internally heated coal carbonization process effluxes the coal gas working method, based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is oxygen rich air and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O is characterized in that comprising following steps:
1. at the first decarbonization process, the dry distillation of coal is effluxed coal gas F000 use at least a portion CO among the unstripped gas F100 as the first decarbonization process unstripped gas F100
2Be removed and obtain the first decarbonization gas TT1Q;
2. at shift conversion step, the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ, becomes " the second decarbonization process " unstripped gas F200 after the conversion gas BHQ cooled dehydrated; Amounts of hydrogen among the conversion gas BHQ: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, " the second decarbonization process " unstripped gas F200 removes hydrogen sulfide, CO at this
2Obtain the second decarbonization gas TT2Q;
4. in the methanation operation, remove that sulphur obtains fine gas JZQ among the second decarbonization gas TT2Q, fine gas JZQ enters the methanation reaction process, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ;
5. in the liquefaction operation, methanation obtains the CH that liquefies through the subcooling process after generating gas SCQ dehydration
4With gas hydrogen.
2. method according to claim 1, it is characterized in that: the dry distillation of coal effluxes coal gas F000 and enters " the first decarbonization process " and become thick desulfurization coal gas CTLQ through wet desulphurization hydrogen operation before, and thick desulfurization coal gas CTLQ makes " the first decarbonization process " unstripped gas F100 and uses.
3. method according to claim 2, it is characterized in that: the dry distillation of coal effluxes coal gas F000 and enters " the first decarbonization process " and pass through before wet desulphurization hydrogen operation, thick desulfurization coal gas CTLQ becomes thick purified gas CJHQ through PSA or TSA detar operation, and thick purified gas CJHQ makes " the first decarbonization process " unstripped gas F100 and uses.
4. method according to claim 1 is based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is purity oxygen and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O is characterized in that:
1. at the first decarbonization process, adopt low pressure VPSA decarbonization process with at least a portion CO among the first decarbonization process unstripped gas F100
2Remove and obtain the first decarbonization gas TT1Q;
2. at shift conversion step, adopt the sulphur resisting and low temp conversing technology, be that 160～360 ℃, pressure are that the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ under 0.6～10.0MPa (absolute pressure) condition in temperature; Amounts of hydrogen among the conversion gas BHQ: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, adopt selectivity to take off H
2S, CO
2Technology makes " the second decarbonization process " unstripped gas F200 finish hydrogen sulfide, CO at this
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, remove that sulphur is down to≤0.1mg/Nm its total sulfur content among the second decarbonization gas TT2Q
3Obtain fine gas JZQ; Fine gas JZQ enters the methanation reaction process, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ;
5. in the liquefaction operation, methanation obtains the CH that liquefies through the subcooling process after generating gas SCQ dehydration
4With gas hydrogen.
5. method according to claim 1 is based on CO
2Be the coal carbonization technique (application number 201110058345.9) of temperature control component in combustion, the oxygenant that dry distillation of coal process is used is purity oxygen and CO
2The mixture of gas, the dry distillation of coal efflux coal gas F000 mainly by H
2, CO, CH
4, CO
2, H
2The compositions such as O is characterized in that:
1. at the first decarbonization process, adopt the VPSA decarbonization process with CO among the unstripped gas F100
2Be removed to≤5 volume % obtain the first decarbonization gas TT1Q, and process operation pressure is lower than 0.3MPa (absolute pressure);
2. at shift conversion step, adopt the sulphur resisting and low temp conversing technology, be that 160～360 ℃, pressure are that the first decarbonization gas TT1Q finishes part CO transformationreation and obtains conversion gas BHQ under 0.8～5.0MPa (absolute pressure) condition in temperature; Amounts of hydrogen among the unstripped gas F200: satisfy the operation hydrogen output requirement of 5. liquefying of 4. methanation operation of step hydrogen-consuming volume and step;
3. at the second decarbonization process, adopting the organic amine aqueous solution is solvent removal hydrogen sulfide and CO
2, make " the second decarbonization process " unstripped gas F200 finish hydrogen sulfide, CO at this
2Remove, obtain the second decarbonization gas TT2Q;
4. in the methanation operation, adopt the zinc oxide desulfurization technology to remove that sulphur obtains fine gas JZQ among the second decarbonization gas TT2Q, fine gas JZQ total sulfur content≤0.1mg/Nm
3Fine gas JZQ enters the methanation reaction process, is under 0.8～5.0MPa (absolute pressure) condition at pressure, makes CO and CO among the fine gas JZQ
2Generate methane with hydrogen reaction, obtain mainly by H
2And CH
4The methanation that forms generates gas SCQ; The CO transformation efficiency is greater than 98 volume %, CO
2Transformation efficiency is greater than 95 volume %.
5. in the liquefaction operation, after methanation generates gas SCQ dehydration, be to obtain LNG and gas hydrogen PH2, the H of gas hydrogen PH2 through the subcooling process under 0.8～5.0MPa (absolute pressure) condition at pressure
2Purity is greater than 95 volume %.
6. it is characterized in that according to claim 4 or 5 described methods:
1. at the first decarbonization process, working pressure is lower than 0.2MPa (absolute pressure);
2. at shift conversion step, working pressure is 0.8～2.0MPa (absolute pressure);
3. at the second decarbonization process, working pressure is 0.8～2.0MPa (absolute pressure), and to adopt Aqueous Activated MethyldiethanolamineSolutions Solutions be the solvent depriving hydrogen sulphide, take off CO
2
4. in the methanation operation, working pressure is 0.8～2.0MPa (absolute pressure);
5. in the liquefaction operation, working pressure is 2.5～5.0MPa (absolute pressure).
7. it is characterized in that according to claim 4 or 5 described methods:
4. in the methanation operation, the CO transformation efficiency is greater than 99 volume %, CO
2Transformation efficiency is greater than 98 volume %;
5. in the liquefaction operation, methanation obtains LNG and gas hydrogen PH2, the H of gas hydrogen PH2 through the subcooling process after generating gas SCQ dehydration
2Purity is greater than 98 volume %.
8. method according to claim 1 is characterized in that:
6. in the hydrogen purification operation, adopt the PSA technology, gas hydrogen PH2 is separated into pure hydrogen CH2 and stripping gas, the H of pure hydrogen CH2
2Purity is greater than 99 volume %.
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| CN112897464A (en) * | 2021-01-18 | 2021-06-04 | 西南化工研究设计院有限公司 | Process for producing hydrogen and coproducing LNG (liquefied Natural gas) by using raw gas with methanation |
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| CN102533365A (en) * | 2011-12-12 | 2012-07-04 | 航天长征化学工程股份有限公司 | Process for coproducing liquefied natural gas (LNG) and synthetic ammonia |
| CN102676251A (en) * | 2012-05-22 | 2012-09-19 | 太原理工大学 | Process for preparing methane by utilizing coke oven gas |
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| CN102676251A (en) * | 2012-05-22 | 2012-09-19 | 太原理工大学 | Process for preparing methane by utilizing coke oven gas |
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| CN112897464A (en) * | 2021-01-18 | 2021-06-04 | 西南化工研究设计院有限公司 | Process for producing hydrogen and coproducing LNG (liquefied Natural gas) by using raw gas with methanation |
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