CN101709226B - Technique for decarburizing Fischer-Tropsch synthetic recycle gas and recovering hydrocarbons - Google Patents
Technique for decarburizing Fischer-Tropsch synthetic recycle gas and recovering hydrocarbons Download PDFInfo
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- CN101709226B CN101709226B CN200910220343A CN200910220343A CN101709226B CN 101709226 B CN101709226 B CN 101709226B CN 200910220343 A CN200910220343 A CN 200910220343A CN 200910220343 A CN200910220343 A CN 200910220343A CN 101709226 B CN101709226 B CN 101709226B
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Abstract
The invention discloses a technique for decarburizing Fischer-Tropsch synthetic recycle gas and recovering hydrocarbons, which is realized in a way that: recycle gas discharged from a Fischer-Tropsch synthetic reaction system firstly enters a pressure swing absorption device to remove CO2; purified gas recovered from the top of the pressure swing absorption device returns to the Fischer-Tropsch synthetic system; and desorbed gas recovered from the bottom is compressed by a compressor, and then processed in a hydrocarbon recovery way orderly through an absorption column, a desorption column and a stabilizer column. The decarbonizing process of the invention adopts a pressure swing absorption and desorption gas pressurization technique; and thus, the invention has the advantages of low energy consumption, no corrosion to equipment and pipelines, and low investment. The absorbed dry gas directly returns to the Fischer-Tropsch synthetic reaction system, thereby enhancing the conversion rate of Fischer-Tropsch synthesis active components and Fischer-Tropsch synthetic gas. The hydrocarbon recovering process adopts a normal temperature oil washing technique, and the operating temperature of the absorption column is -10-60 DEG C; and the three-column process is adopted, thereby having the advantages of low investment, low energy consumption and no loss of absorbent.
Description
One, technical field
The invention belongs to the Fischer-Tropsch synthesis technical field, be specifically related to a kind of Fischer-Tropsch synthesis circulation gas carbonic acid gas and hydro carbons and reclaim technology.
Two, background technology
Oil is the goods and materials commodity of a national strategy property.China is a rich coal, oil-poor country, and petroleum resources are rare, and annual import substantial oil is to satisfy the demand that national economy increases.Therefore, seeking substitute energy is the problem of a national strategy property.Fischer-Tropsch synthesis process is to use coal or Sweet natural gas to be bonded into liquid fuel as stock yard, H in fischer-tropsch reaction
2When on going back the ortho states catalyzer, generating hydrocarbon product with CO, in reaction process, generate water simultaneously, water carries out water gas shift reaction and generates a large amount of CO with CO again
2Therefore, the gas that goes out synthesis reactor is after with product separation wherein, and remaining tail gas is as circulation gas, and a part must be through taking off CO
2After return the Fischer-Tropsch synthesis system and reuse.Another part goes out the Fischer-Tropsch synthesis system, and adopt to reclaim technology wherein hydro carbons is reclaimed.At present, the hot carbon potassium of Benfield catalysis decarbonization process is mainly adopted in the decarburization of Fischer-Tropsch synthetic gas, and its solution regeneration hear rate of the typical hot salt of wormwood decarbonization process of U.S. Benfield catalysis is about 5.02 * 10
3KJ/Nm
3CO
2, energy consumption is bigger, and equipment and pipeline corrosion are serious, and investment is high, effectively synthesis gas components (CO and H
2) return less than in the Fischer-Tropsch synthesis, the virgin gas utilization ratio is low; Hydro carbons reclaims the main low temperature oil wash technology that adopts, and the absorption tower service temperature needs to consume great amount of cold at-30～-20 ℃, and equipment also will adopt anti-low temperature material, and investment is high, and adopts four-column process flow, and not only absorption agent loses easily, and energy consumption is higher.
Three, summary of the invention
The purpose of this invention is to provide a kind of Fischer-Tropsch synthesis circulation gas carbonic acid gas and hydro carbons and reclaim technology, this technology can overcome many deficiencies of the prior art effectively.
Be to realize above-mentioned purpose, the technical scheme that the present invention adopts is: this technology is that the circulation gas that the Fischer-Tropsch synthesis system is introduced into the transformation adsorber and takes off CO
2, return the Fischer-Tropsch synthesis system from the purified gas of transformation adsorber recovered overhead, the stripping gas that reclaim the bottom after compressor compresses, successively through the absorption tower, desorption tower and stabilizer tower carry out hydro carbons and reclaim.
Above-mentioned transformation adsorber is PSA-CO
2/ R transformation adsorber.
Above-mentioned transformation adsorber inlet working pressure is 1.0-4.0Mpa, and temperature is 0-80 ℃.
Above-mentioned purified gas is 0.98-3.98Mpa from transformation absorption device output pressure.
Above-mentioned stripping gas is 0.005-0.05Mpa from transformation absorption device output pressure.
Above-mentioned absorption tower reflux to absorb the hydro carbons in the gas through absorption agent, and its working pressure is 1.0-3.0Mpa, and temperature is-10-60 ℃; Absorption agent is petroleum naphtha, gasoline, kerosene or diesel oil distillate.
The working pressure of above-mentioned desorption tower is 1.05-3.1Mpa, and temperature is 0-220 ℃.
The working pressure of aforementioned stable tower is 1.05-2.5Mpa, and temperature is 30-220 ℃.
Carbon rejection process of the present invention adopts transformation absorption and stripping gas pressing technology, and energy consumption is low, and equipment and pipeline do not have corrosion, invest lowly, absorption back dry gas directly returns the Fischer-Tropsch synthesis system, has improved the transformation efficiency that Fischer-Tropsch synthesizes active principle and Fischer-Tropsch synthetic gas; The hydro carbons removal process adopts normal temperature oil wash technology, and the absorption tower service temperature be-10-60 ℃, and the employing three-column process flow, less investment, energy consumption is low, and absorption agent does not lose.Below two forms be respectively and adopt the forward and backward gas composition of technology of the present invention:
Fischer-Tropsch circulation gas is formed as follows:
| Component | H 2 | N 2+CH 4 | C 2H 6 | C 3H 8 | C 4H 10 | C 5 | CO | CO 2 | ∑ |
| ?(v％) | 36.47 | 15.69 | 5.31 | 4.97 | 2.48 | 1.23 | 16.27 | 17.58 | 100.00 |
Decarburization after gas is formed as follows:
| Component | H 2 | N 2+CH 4 | C 2H 6 | C 3H 8 | C 4H 10 | C 5 | CO | CO 2 | ∑ |
| ?(v％) | 57.72 | 20.48 | 0 | 0 | 0 | 0 | 21.23 | 0.57 | 100.00 |
[0017]The process method that adopts decarburization of the present invention and hydro carbons to reclaim, the purified gas CO after the decarburization
2Concentration is reduced to below 1.5%, and the hydro carbons recovery reaches 95%.
Four, embodiment
Technology of the present invention comprises PSA-CO
2Equipment such as/R transformation adsorber, compressor, absorption tower, desorption tower, stabilizer tower, water cooler and pump.Come from the 2.48Mpa of Fischer-Tropsch synthesis system, 35 ℃ circulation gas at first gets into PSA-CO
2/ R transformation adsorber removes the CO in the circulation gas
2CO from absorption device recovered overhead
2Concentration is returned the repeated use of Fischer-Tropsch synthesis system less than 1.5% purified gas.The 0.05Mpa that reclaims from adsorber bottom, 40 ℃ of stripping gass to 1.5Mpa, get into the absorption tower through compressor compresses.The 1.45MPa of top, absorption tower output, 50 ℃ of gases get into the burning gas system, and oil gets into desorption tower through pump at the bottom of the tower; The 1.65MPa of desorption tower top output, 62 ℃ of gases are sent into the bottom, absorption tower again and are carried out the secondary absorption.1.65MPa, oil gets into stabilizer tower at the bottom of 62 ℃ the tower; The 1.50MPa of stabilizer tower top output, 74 ℃ of gases get into return tank of top of the tower after the cat head water cooler is cooled to 40 ℃, a part refluxes as stabilizer tower, and another one delivers to outside the system as the liquefied gas component.Oil is after water cooler cooling at the bottom of the stabilizer tower at the bottom of the tower, and a part gets into the absorption tower as absorption agent, and another part goes out device as naphtha product.
Claims (4)
1. Fischer-Tropsch synthesis circulation gas carbonic acid gas and hydro carbons reclaim technology; This technology is that the circulation gas that the Fischer-Tropsch synthesis system is introduced into the transformation adsorber and takes off CO2; Return the Fischer-Tropsch synthesis system from the purified gas of transformation adsorber recovered overhead; The stripping gas that reclaim the bottom after compressor compresses, successively through the absorption tower, desorption tower and stabilizer tower carry out hydro carbons and reclaim;
Described transformation adsorber is a PSA-CO2/R transformation adsorber;
Described transformation adsorber inlet working pressure is 1.0-4.0Mpa, and temperature is 0-80 ℃;
Described purified gas is 0.98-3.98Mpa from transformation absorption device output pressure;
Described stripping gas is 0.005-0.05Mpa from transformation absorption device output pressure.
2. a kind of Fischer-Tropsch synthesis circulation gas carbonic acid gas according to claim 1 and hydro carbons reclaim technology, it is characterized in that refluxing through absorption agent in described absorption tower to absorb the hydro carbons in the gas, and its working pressure is 1.0-3.0Mpa, and temperature is-10-60 ℃; Absorption agent is petroleum naphtha, gasoline, kerosene or diesel oil distillate.
3. a kind of Fischer-Tropsch synthesis circulation gas carbonic acid gas according to claim 1 and 2 and hydro carbons reclaim technology, and the working pressure that it is characterized in that described desorption tower is 1.05-3.1Mpa, and temperature is 0-220 ℃.
4. a kind of Fischer-Tropsch synthesis circulation gas carbonic acid gas according to claim 1 and 2 and hydro carbons reclaim technology, and the working pressure that it is characterized in that described stabilizer tower is 1.05-2.5Mpa, and temperature is 30-220 ℃.
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| CN101709226B true CN101709226B (en) | 2012-10-03 |
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| CN103509582A (en) * | 2012-06-26 | 2014-01-15 | 中科合成油工程有限公司 | Method for producing synthetic oil products and chemical products |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003016250A1 (en) * | 2001-08-17 | 2003-02-27 | Johnson Matthey Plc | Production of hydrocarbons |
| CN1944358A (en) * | 2006-09-05 | 2007-04-11 | 上海兖矿能源科技研发有限公司 | Method for recovering low carbon hydrocarbon from Fischer-Tropsch process exhaust |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003016250A1 (en) * | 2001-08-17 | 2003-02-27 | Johnson Matthey Plc | Production of hydrocarbons |
| CN1944358A (en) * | 2006-09-05 | 2007-04-11 | 上海兖矿能源科技研发有限公司 | Method for recovering low carbon hydrocarbon from Fischer-Tropsch process exhaust |
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Owner name: LIAONING BRANCH OF CHINA HUANQIU CONTRACTING + ENG Free format text: FORMER OWNER: FUSHUN BRANCH, CHINA PETROLEUM GROUP ENGINEERING DESIGN CO., LTD. Effective date: 20140530 |
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Effective date of registration: 20140530 Address after: 113006 Liaoning province Fushun City River Road No. 16 Patentee after: Liaoning Branch,China Huanqiu Engineering Co., Ltd. Patentee after: Chengdu Huaxi Chemical Technology Co., Ltd. Address before: 113006 Liaoning province Fushun City River Road No. 16 Patentee before: Fushun Branch, China Petroleum Group Engineering Design Co., Ltd. Patentee before: Chengdu Huaxi Chemical Technology Co., Ltd. |