CN108545696A - A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique - Google Patents
A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique Download PDFInfo
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- CN108545696A CN108545696A CN201810396980.XA CN201810396980A CN108545696A CN 108545696 A CN108545696 A CN 108545696A CN 201810396980 A CN201810396980 A CN 201810396980A CN 108545696 A CN108545696 A CN 108545696A
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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
- C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/044—Selective oxidation of carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of Water gas shift/WGS gas ammonia synthesis gas techniques, after conversion gas fine de-sulfur, gas componant is 52% or more hydrogen, 7% or less nitrogen, 0.1% oxygen, 0.2% or less carbon monoxide, 40% or more carbon dioxide, first carbon dioxide removal is less than 2% to concentration, referred to as thick degassing, it is added and converts required excessive by 0.1% purity oxygen of oxygen or same equivalent air than carbon monoxide, it sets up catalyzing carbon monoxide and is converted to carbon dioxide step, it is to be converted to carbon dioxide by 0.2% or less carbonomonoxide concentration, carbon monoxide residual concentration reaches 1ppm or less, pneumatic transmission essence deoxygenation step will be converted, pressure-variable adsorption essence carbon dioxide removal and carbon monoxide to 10ppm or less are sent again, as ammonia synthesis gas.
Description
Technical field
The present invention relates to chemical industry, energy-saving and environmental protection fields, are a kind of reduction pressure swing adsorption hydrogen production devices, thus reduce ammino
At the method for investment.
Background technology
It is general for the manufacturing method of ammonia synthesis gas for producing the process of synthesis ammonia using Water gas shift/WGS gas as raw material
Using two methods.
A kind of method is after conversion gas fine de-sulfur, will to send PSA decarbonization devices, and decarbonization device is using aluminium oxide, silica gel, activity
Charcoal, molecular sieve carbon dioxide removal make carbon dioxide reach 0.8% hereinafter, send pressure swing adsorption hydrogen production device high purity hydrogen,
Carbon monoxide is less than 10ppm with carbon dioxide mix concentration in hydrogen, and practical hydrogen yield reaches 93% or so, if using recycling
Device can make hydrogen recovery rate reach 98%, and nitrogen does not recycle.
A kind of method is that methanol after conversion gas fine de-sulfur, will be sent to wash decarbonization device, and decarbonization device is removed using refrigerated methanol
Carbon dioxide makes carbon dioxide reach 1ppm hereinafter, liquor charging nitrogen washes removal of carbon monoxide to 9ppm or less.
PSA hydrogen manufacturing and liquid nitrogen washing hydrogen manufacturing nitrogen have larger hydrogen loss all 2% or more, and nitrogen losses are even more pole
Greatly, thus waste energy is very big.
Invention content
It is easy to reach process, PSA hydrogen manufacturing and liquid nitrogen washing hydrogen manufacturing nitrogen that Water gas shift/WGS, which reaches 0.2% or less carbon monoxide,
Hydrogen and nitrogen losses are all very big.The method of the present invention actually replaces hydrogen with carbon monoxide conversion oxygen and converts an oxygen
When changing carbon, pressure-variable adsorption while removal of carbon monoxide with carbon dioxide, nitrogen losses are big, and the individually absorption of carbon dioxide removal
Agent can greatly improve the yield of hydrogen and nitrogen, remove with carbon dioxide removal simultaneously compared with the adsorbent of carbon monoxide
Liquid nitrogen washing workshop section can largely reduce investment, reduce hydrogen and nitrogen losses.
The present invention is a kind of Water gas shift/WGS gas ammonia synthesis gas technique, it is characterised in that：After conversion gas fine de-sulfur, gas
Body ingredient is 52% or more hydrogen, 7% or less nitrogen, 0.1% oxygen, 0.2% or less carbon monoxide, 40% or more titanium dioxide
Carbon, first carbon dioxide removal to concentration are less than 2%, and referred to as thick degassing is added more excessive by 0.1% than oxygen needed for carbon monoxide conversion
Purity oxygen or same equivalent air, set up catalyzing carbon monoxide and be converted to carbon dioxide step, 0.2% or less carbon monoxide is dense
For degree to be converted to carbon dioxide, carbon monoxide residual concentration reaches 1ppm hereinafter, pneumatic transmission essence deoxygenation step will be converted, then send transformation
The smart carbon dioxide removal of absorption is with carbon monoxide to 10ppm hereinafter, becoming ammonia synthesis gas.
Specific implementation mode
Embodiment 1：Water gas shift/WGS gas total amount is 36000NM3/H, 0.84MPa, and after fine de-sulfur, gas componant is hydrogen
50%, nitrogen 7%, carbon monoxide 0.2%, carbon dioxide 42.7%, purity oxygen 18NM3/H is added in oxygen 0.1%, referred to as former
Expect gas.First carbon dioxide removal is less than 2% to concentration, and referred to as thick degassing send thick degassing to enter preheater, improves gas temperature and arrive
130~180 DEG C, it is sent into carbon monoxide converter conversion carbon monoxide (oxygen excessive 30% or more), exports carbonomonoxide concentration
Reach 1ppm hereinafter, recycling reaction gas heat manufacture vapor, is re-fed into smart deoxidation reactor, makes remnant oxygen and excess hydrogen
Reaction obtains the gas that oxygen concentration is less than 1ppm, and recycling heat of reaction manufactures vapor, and the cooling gas send change to room temperature
It presses adsorbent equipment essence carbon dioxide removal to be less than 10ppm to carbon monoxide and concentration of total carbon dioxide, removes water dew point to -70 DEG C,
Pressure-variable adsorption exit gas ingredient is hydrogen 75%, and nitrogen 25%, oxygen 1ppm is hereinafter, carbon monoxide and total carbon dioxide capacity
10ppm is hereinafter, water water dew point to -70 DEG C, obtains ammonia synthesis gas processed.
Embodiment 2：Water gas shift/WGS gas total amount is 36000NM3/H, 1.84MPa, and after fine de-sulfur, gas componant is hydrogen
54%, nitrogen 5%, carbon monoxide 0.1%, carbon dioxide 41.8%, oxygen 0.1%, addition purity oxygen 9NM3/H, referred to as raw material
Gas.First carbon dioxide removal is less than 2% to concentration, and referred to as thick degassing send thick degassing to enter preheater, improves gas temperature and arrive
130~180 DEG C, it is sent into carbon monoxide converter conversion carbon monoxide (oxygen excessive 30% or more), exports carbonomonoxide concentration
Reach 1ppm hereinafter, recycling reaction gas heat manufacture vapor, is re-fed into smart deoxidation reactor, makes remnant oxygen and excess hydrogen
Reaction obtains the gas that oxygen concentration is less than 1ppm, and recycling heat of reaction manufactures vapor, and the cooling gas send change to room temperature
It presses adsorbent equipment essence carbon dioxide removal to be less than 10ppm to carbon monoxide and concentration of total carbon dioxide, removes water dew point to -70 DEG C,
Pressure-variable adsorption exit gas ingredient is hydrogen 75%, and nitrogen 25%, oxygen 1ppm is hereinafter, carbon monoxide and total carbon dioxide capacity
10ppm is hereinafter, water water dew point to -70 DEG C, obtains ammonia synthesis gas processed.
Embodiment 3：Semiwater gas conversion gas total amount is 36000NM3/H, 2.84MPa, and after fine de-sulfur, gas componant is hydrogen
Purity oxygen 284NM3/H is added, referred to as in gas 54%, nitrogen 4%, carbon monoxide 0.4%, carbon dioxide 40.5%, oxygen 0.1%
Unstripped gas.First carbon dioxide removal is less than 2% to concentration, and referred to as thick degassing send thick degassing to enter preheater, improves gas temperature
To 130~180 DEG C, it is sent into carbon monoxide converter conversion carbon monoxide (oxygen excessive 30% or more), outlet carbon monoxide is dense
Degree reaches 1ppm hereinafter, recycling reaction gas heat manufacture vapor, is re-fed into smart deoxidation reactor, makes remnant oxygen and excessive hydrogen
Solid/liquid/gas reactions obtain the gas that oxygen concentration is less than 1ppm, and recycling heat of reaction manufactures vapor, and the cooling gas is sent to room temperature
Pressure-swing absorption apparatus essence carbon dioxide removal is less than 10ppm, removing water dew point to -70 to carbon monoxide and concentration of total carbon dioxide
DEG C, pressure-variable adsorption exit gas ingredient is hydrogen 75%, and nitrogen 25%, oxygen 1ppm is hereinafter, carbon monoxide is total with carbon dioxide
Amount 10ppm is hereinafter, water water dew point to -70 DEG C, obtains ammonia synthesis gas processed.
Claims (1)
1. a kind of Water gas shift/WGS gas ammonia synthesis gas technique, it is characterised in that：After conversion gas fine de-sulfur, gas componant is
52% or more hydrogen, 7% or less nitrogen, 0.1% oxygen, 0.2% or less carbon monoxide, 40% or more carbon dioxide first remove
Carbon dioxide is less than 2% to concentration, and the purity oxygen more excessive by 0.1% than oxygen needed for carbon monoxide conversion is added in referred to as thick degassing
Or same equivalent air, it sets up catalyzing carbon monoxide and is converted to carbon dioxide step, be conversion by 0.2% or less carbonomonoxide concentration
At carbon dioxide, carbon monoxide residual concentration reaches 1ppm hereinafter, pneumatic transmission essence deoxygenation step will be converted, then send pressure-variable adsorption essence de-
Carbon dioxide is with carbon monoxide to 10ppm hereinafter, becoming ammonia synthesis gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810396980.XA CN108545696A (en) | 2018-04-27 | 2018-04-27 | A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810396980.XA CN108545696A (en) | 2018-04-27 | 2018-04-27 | A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique |
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| CN201810396980.XA Withdrawn CN108545696A (en) | 2018-04-27 | 2018-04-27 | A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937573A (en) * | 2019-10-28 | 2020-03-31 | 中科液态阳光(苏州)氢能科技发展有限公司 | Hydrogen mixed residual gas reforming method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4572829A (en) * | 1984-11-09 | 1986-02-25 | Union Carbide Corporation | Ammonia synthesis gas purification |
| CN104560201A (en) * | 2013-10-25 | 2015-04-29 | 昊华工程有限公司 | Production process and system of high-purity hydrogen and ammonia synthesis process and system |
| CN107244651A (en) * | 2017-06-09 | 2017-10-13 | 杨皓 | A kind of blast furnace tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
-
2018
- 2018-04-27 CN CN201810396980.XA patent/CN108545696A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4572829A (en) * | 1984-11-09 | 1986-02-25 | Union Carbide Corporation | Ammonia synthesis gas purification |
| CN104560201A (en) * | 2013-10-25 | 2015-04-29 | 昊华工程有限公司 | Production process and system of high-purity hydrogen and ammonia synthesis process and system |
| CN107244651A (en) * | 2017-06-09 | 2017-10-13 | 杨皓 | A kind of blast furnace tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110937573A (en) * | 2019-10-28 | 2020-03-31 | 中科液态阳光(苏州)氢能科技发展有限公司 | Hydrogen mixed residual gas reforming method |
| CN110937573B (en) * | 2019-10-28 | 2023-08-22 | 中科液态阳光(苏州)氢能科技发展有限公司 | Hydrogen mixed residual gas reforming method |
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Application publication date: 20180918 |