WO2012132336A1 - 重質炭化水素の除去方法 - Google Patents
重質炭化水素の除去方法 Download PDFInfo
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- WO2012132336A1 WO2012132336A1 PCT/JP2012/001965 JP2012001965W WO2012132336A1 WO 2012132336 A1 WO2012132336 A1 WO 2012132336A1 JP 2012001965 W JP2012001965 W JP 2012001965W WO 2012132336 A1 WO2012132336 A1 WO 2012132336A1
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/02—Stabilising gasoline by removing gases by fractioning
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/14—Hydrocarbons
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
- C10G5/04—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas with liquid absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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Definitions
- the present invention relates to a method for removing heavy hydrocarbons contained in offgas when the offgas generated in the Fischer-Tropsch reaction step in the GTL process is used as a fuel gas in the synthesis gas production step.
- Natural gas does not generate sulfur oxides or particulate matter that cause air pollution even when burned, and generates less carbon dioxide per calorific value. It is considered to be a low fuel system.
- GTL gas-to-liquid technology
- a method for producing liquid synthetic hydrocarbons such as naphtha, kerosene and light oil by chemical reaction using natural gas as a raw material is known as a method for producing liquid synthetic hydrocarbons such as naphtha, kerosene and light oil by chemical reaction using natural gas as a raw material.
- GTL technology is mainly composed of straight-chain hydrocarbons by the process of producing synthesis gas (mixed gas of carbon monoxide and hydrogen) by a reforming reaction (synthesis gas production process) and the Fischer-Tropsch (FT) synthesis reaction.
- the process comprises producing a synthetic oil from synthetic gas (FT synthesis process), and hydrotreating and hydrocracking the synthetic oil to obtain a product oil (upgrading process).
- Syngas is produced by a reforming reaction of natural gas.
- Technologies for producing synthesis gas using reforming reactions include steam reforming, CO 2 reforming, autothermal reforming (ATR), catalytic partial oxidation (CPOX), and direct partial oxidation ( POX) and the like are known.
- the reforming reaction includes, in principle, a steam reforming reaction in which steam is added to natural gas to generate synthesis gas according to the following reaction formula (1), and carbon dioxide is added to natural gas or included in natural gas.
- the carbon dioxide is roughly classified into a carbon dioxide reforming reaction that generates synthesis gas according to the following reaction formula (2).
- the reforming reaction of methane mainly contained in natural gas is shown as an example.
- these reforming reactions are endothermic reactions, and it is necessary to supply heat necessary for the reaction from the outside.
- ATR, CPOX, and POX a part of natural gas as a raw material is completely oxidized using a burner, a catalyst, etc., respectively, and modified using heat generated when carbon dioxide and water are produced from hydrocarbons such as methane. Have a quality reaction. Therefore, the entire system becomes an exothermic reaction, and it is not necessary to introduce necessary heat from the outside.
- a tubular reformer filled with a catalyst is installed in a heating furnace, and heat necessary for the reforming reaction is supplied from the outside by a heating means such as burner combustion. is doing.
- ATR and POX are particularly suitable for large-scale manufacturing.
- ATR and POX include a process of adding oxygen to natural gas, an expensive oxygen plant is required. Furthermore, since the addition of oxygen to natural gas causes a large amount of heat generation, there is a risk of explosion and the restrictions on the design and operation of the plant are large.
- the steam reforming method and the CO 2 reforming method do not introduce oxygen into natural gas, and the reaction itself is an endothermic reaction, so that there is an advantage that the synthesis gas can be produced more safely. Further, by simultaneously performing the steam reforming method and the CO 2 reforming method, the hydrogen / carbon monoxide ratio of the generated synthesis gas can be brought close to 2.0 which is preferable in the FT synthesis reaction.
- the FT off-gas generated in the FT synthesis process which is a subsequent process, is reused as fuel for heating the tubular reformer.
- the energy efficiency of the entire GTL process can be improved.
- the FT off-gas is a gas composed of unreacted synthesis gas, methane or the like generated in the FT synthesis step.
- reaction formula (3) one unit of a hydrocarbon chain (—CH 2 —) is generated from hydrogen and carbon monoxide, and this is synthesized to grow a hydrocarbon chain.
- This reaction is an exothermic reaction as a whole, and is represented by the following reaction formula (3).
- the number of carbon atoms of the hydrocarbon generated in the FT synthesis reaction is not constant, and hydrocarbons having various degrees of polymerization (n number) are generated.
- the ratio of the generated (—CH 2 —) to be used for the growth of the hydrocarbon chain is referred to as chain growth probability ⁇ , and the degree of polymerization of which degree of hydrocarbon chain is generated is determined by the chain growth probability ⁇ (Anderson- Schulz-Flory distribution).
- ⁇ > 0.85 which increases the kerosene oil fraction, which is the main target of GTL, and the wax fraction, which is heavier and can obtain kerosene and diesel oil by decomposition, increases.
- the reaction is carried out at ⁇ > 0.90. However, there are a few light hydrocarbons that did not grow well in this region. Also, not all of the synthesis gas is used for the reaction, and some of the hydrogen and carbon monoxide remain unreacted.
- Hydrocarbons having a high carbon number and a high boiling point which are the objects of the FT synthesis reaction, are taken out as liquid components.
- Light hydrocarbons such as H 2 O, methane and ethane, which are by-products of the reaction, and unreacted hydrocarbons are extracted.
- Hydrogen, carbon monoxide, and the like are taken out as a mixed gaseous component.
- H 2 O and the like were removed by cooling and condensing this gaseous component with cooling water or the like, and did not condense.
- a gas composed of hydrogen, carbon monoxide, methane, ethane, a hydrocarbon having a low boiling point, and the like is recycled to the FT synthesis reaction.
- methane or the like does not react any more when it is introduced into the FT synthesis reaction, the ratio of methane or the like contained in the gaseous component increases every time recycling is repeated.
- FT off-gas a part of the gas is extracted before being recycled and removed as off-gas (FT off-gas).
- the FT off-gas generated in this way contains a large amount of combustible components such as methane, and therefore can be used as a fuel for heating the tubular reformer.
- the FT off-gas contains a small amount of heavy hydrocarbons that are products of the FT synthesis reaction.
- heavy hydrocarbons having 5 or more carbon atoms may be thermally decomposed, polymerized, or the like when heated to be precipitated as a liquid or solid substance. Therefore, when off gas is used as fuel for tube reformer heating as it is, the precipitated heavy hydrocarbon may block the heating burner tip, hindering stable heating by the burner, and reducing the efficiency of the GTL process. is there.
- the present invention reacts natural gas mainly composed of methane with steam and / or carbon dioxide gas through a tubular reformer that is filled with a reforming catalyst and heated to thereby produce hydrogen and carbon monoxide as main components.
- the method for producing hydrogen oil heavy hydrocarbons contained in the FT off-gas are removed. Removed by It is a method characterized by using the FT offgas after the removal as a fuel for tubular reformer.
- the means of the present invention heavy hydrocarbons having 5 or more carbon atoms contained in the FT off-gas are removed before being supplied to the burner, so that the burner tip is not blocked by thermal decomposition or polymerization. This makes it possible to operate the tube reformer over a long period of time. Furthermore, since the FT off gas can be effectively used as a fuel, the energy efficiency of the entire GTL technology is improved.
- FIG. 1 The figure which shows the removal method of the heavy hydrocarbon which concerns on Example 1.
- FIG. 2 The figure which shows the removal method of the heavy hydrocarbon which concerns on Example 2.
- FIG. 3 The figure which shows the removal method of the heavy hydrocarbon which concerns on Example 3.
- FIG. 4 The figure which shows the removal method of the heavy hydrocarbon which concerns on Example 4.
- FIG. 5 The figure which shows the removal method of the heavy hydrocarbon which concerns on Example 5.
- the synthesis gas produced by the reforming reaction flows into the bubble column reactor installed in the FT synthesis process from the bottom.
- the bubble column reactor is filled with a slurry composed of liquid hydrocarbons and catalyst particles, which are products of the FT synthesis reaction, and when the synthesis gas rises in the contained slurry, carbon monoxide Hydrocarbons are produced by the FT synthesis reaction using hydrogen and hydrogen gas.
- the liquid hydrocarbon among the synthesized hydrocarbons is introduced into the separator together with the catalyst particles as a slurry, where it is separated into a solid component such as catalyst particles and a liquid component containing liquid hydrocarbons.
- the separated solid component is returned to the bubble column reactor.
- Liquid components are supplied to the rectification tower and heated, and due to differences in boiling point, naphtha fraction (boiling point is about 150 ° C or less), kerosene / light oil fraction (boiling point is about 150 to 350 ° C), and wax fraction Fraction (boiling point is about 350 ° C. or higher). Each fraction is then sent to the upgrade process.
- gaseous components including gaseous components of unreacted synthesis gas and synthesized hydrocarbon are released from the top of the bubble column reactor and supplied to the hydrocarbon recovery device.
- the hydrocarbon recovery device is not particularly limited.
- the gaseous component is cooled by a heat exchanger using cooling water, and is not condensed with a liquid component composed of condensed water and liquid hydrocarbon. Separated into gaseous components. Water is removed from the separated liquid component, and the hydrocarbon is introduced into the rectification column.
- the gaseous components remaining after separation in the hydrocarbon recovery device are mainly composed of unreacted synthesis gas and light hydrocarbons such as methane and ethane, but contain a small amount of heavy hydrocarbons.
- This gaseous component is reintroduced into the bottom of the bubble column reactor and reused in the FT synthesis reaction, but prevents any further methane, ethane, etc. from accumulating in the bubble column reactor. Therefore, a part is extracted and discharged as off-gas (FT off-gas), and used as a fuel gas for heating the tubular reformer for reforming reaction in the synthesis gas production process.
- FT off-gas off-gas
- the FT off-gas thus exhausted and recycled as the fuel gas for the reforming reaction also contains a small amount of heavy hydrocarbons.
- This heavy hydrocarbon is deposited by pyrolysis, polymerization, etc. when used as fuel gas, clogs the burner tip, and hinders stable heating of the tubular reformer over a long period of time. .
- the present invention removes heavy hydrocarbons contained in the gas before using the FT off-gas as fuel for the tubular reformer.
- the first embodiment of the present invention is a method of absorbing heavy hydrocarbons in offgas by absorbing oil by bringing FT offgas into direct contact with the absorbing oil.
- the absorbing oil is not particularly limited as long as it can absorb hydrocarbons having 5 or more carbon atoms contained in the FT offgas, but it is preferable to use relatively heavy kerosene or light oil.
- a kerosene fraction or a light oil fraction which is the final product of the GTL process, can be used, and if there is an appropriate intermediate oil during the GTL process, it may be used.
- an intermediate oil kerosene / light oil fractions fractionated in the rectification tower, hydrorefined products thereof, and the like can be used.
- the absorption conditions are not particularly limited, and can be suitably set depending on the absorption oil used. However, in order to prevent the absorption oil from evaporating, it is preferable that the temperature is around 10 to 50 ° C. and the pressure is 2.4 to 3.2 MPaG.
- the second embodiment of the present invention is a method of introducing FT offgas into a distillation column and distilling and separating heavy hydrocarbons.
- the distillation column is not particularly limited as long as it can separate hydrocarbons having 5 or more carbon atoms contained in the FT offgas by distillation.
- a distillation column may be newly installed, or if there is a distillation column capable of separating hydrocarbons having 5 or more carbon atoms in the process, it may be introduced there.
- Good for example, in an upgrading process, a product (hydrogenated naphtha) obtained by hydrotreating a naphtha fraction supplied from the upper part of the rectifying column is separated into liquid naphtha and gas mainly composed of light hydrocarbons.
- a distillation column is used.
- An FT off-gas can be introduced into the distillation column, and the separated gas can be used as a fuel for the tubular reformer.
- the distillation conditions are not particularly limited. For example, it is preferable to distill at a column top temperature of ⁇ 50 to 40 ° C. and a pressure of 2.4 to 3.2 MPaG.
- the third embodiment of the present invention is a method for cooling and separating FT offgas and condensing heavy hydrocarbons.
- the cooling conditions are not particularly limited as long as hydrocarbons having 5 or more carbon atoms contained in the FT off-gas can be separated.
- the temperature is 5 to 20 ° C.
- the pressure is 2.4 to 3. 2 MPaG is preferable.
- the cooling method is not particularly limited, and for example, a heat exchanger using cooling water or waste water generated in the process can be used.
- the fourth embodiment of the present invention is a method for removing heavy hydrocarbons from FT offgas by an adsorbent.
- the adsorbent is not particularly limited as long as it can separate hydrocarbons having 5 or more carbon atoms contained in the FT offgas.
- a method of adsorbing with activated carbon can be used.
- the conditions for adsorption are preferably a temperature of 20 to 40 ° C. and a pressure of 0 to 3.2 MPaG.
- the activated carbon is preferably regenerated by a steaming treatment at 100 to 150 ° C. and 0 to 0.35 MPaG. At that time, for example, if two adsorption towers are installed in the GTL process and the operation is switched between adsorption and regeneration, continuous operation is possible.
- the first to fourth embodiments are not necessarily used alone.
- the FT off-gas is cooled (second embodiment) and brought into contact with the absorbent (first embodiment) or an adsorbent (fourth embodiment) is used, a superimposed effect can be obtained. It is preferable because it is expected.
- Example 1 In a plant executing the GTL technology, a gas composed of unreacted synthesis gas and gaseous hydrocarbons generated in the FT synthesis step was cooled and gas-liquid separated to obtain an FT off-gas having the composition shown in Table 1.
- Cn means a hydrocarbon having n carbon atoms
- C5 + means a hydrocarbon having 5 or more carbon atoms.
- the temperature of the obtained FT offgas was 45 ° C.
- the pressure was 2.75 MPaG
- the content of heavy hydrocarbons having 5 or more carbon atoms was 4.32 wt%.
- This FT off-gas is cooled to 10 ° C. at a pressure of 2.7 MPaG and separated into a condensed liquid component and a non-condensed fuel gas to recover heavy hydrocarbons contained in the liquid component (FIG. 1). Thereafter, the content of heavy hydrocarbons having 5 or more carbon atoms contained in the fuel gas was measured.
- Example 2 The FT offgas obtained in Example 1 was introduced into a distillation column and separated into a fuel gas recovered from the column top and a liquid component recovered from the column bottom (FIG. 2).
- the pressure at the top of the FT offgas was 2.65 MPaG
- the temperature at the bottom was 198 ° C.
- the temperature at the top was ⁇ 37 ° C. Thereafter, the content of heavy hydrocarbons having 5 or more carbon atoms contained in the fuel gas obtained from the tower top was measured.
- Example 3 The FT offgas obtained in Example 1 and the absorbing oil corresponding to the light oil were directly contacted in a single stage under the conditions of FT offgas pressure of 2.7 MPaG and temperature of 48 ° C., and heavy carbonization absorbed in the absorbing oil. Hydrogen was recovered (Figure 3). Table 2 shows the distillation properties of the absorption oil used. Further, the flow rate of the absorbing oil was set to 10,000 kg / h. Thereafter, the content of heavy hydrocarbons having 5 or more carbon atoms that were not absorbed by the absorbing oil contained in the fuel gas was measured.
- Example 4 In Example 3, the temperature at the time of contacting with the absorbing oil was further cooled to 10 ° C., and heavy hydrocarbons were recovered (FIG. 4). The flow rate of the absorbing oil was 10,000 kg / h. Thereafter, the content of heavy hydrocarbons having 5 or more carbon atoms that were not absorbed by the absorbing oil contained in the fuel gas was measured.
- Example 5 In Example 3, the FT offgas and the absorbing oil were brought into contact with each other using an eight-stage absorption tower to recover heavy hydrocarbons (FIG. 5).
- the pressure of the FT offgas was 2.65 MPaG at the top of the column, and the temperature was 49 ° C. at the bottom and 50 ° C. at the top. Further, the flow rate of the absorbing oil was set to 10,000 kg / h. Thereafter, the content of heavy hydrocarbons having 5 or more carbon atoms that were not absorbed by the absorbing oil contained in the fuel gas was measured.
- Examples 6 to 8 In Examples 3 to 5, experiments were performed under the same conditions except that the flow rate of the absorbing solution used was doubled to 20000 kg / h, and Examples 6 to 8 were obtained, respectively.
- the content of heavy hydrocarbons having 5 or more carbon atoms contained in the fuel gas after the removal treatment of heavy hydrocarbons, the flow rate of the recovered or absorbed liquid, and the heavy gas contained in the FT off-gas Table 3 shows the ratio of the distribution of the quality hydrocarbons to the fuel gas and the recovered liquid or absorbent. In any of the examples, the effect of removing heavy hydrocarbons from the fuel gas was confirmed.
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- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
ΔH298=+206kJ/mol
式(2): CH4 + CO2 → 2CO + 2H2
ΔH298=+248kJ/mol
ΔH298=-167kJ/mol-CO
本発明の第1の実施形態は、FTオフガスを吸収油と直接接触させることにより、オフガス中の重質炭化水素を吸収油に吸収させる方法である。
GTL技術を実行するプラントにおいて、FT合成工程で発生した未反応合成ガスと気体状の炭化水素からなるガスを冷却して気液分離し、表1に示す組成を有するFTオフガスを得た。なお、表1においてCnは炭素数がn個の炭化水素を意味し、C5+は、炭素数が5個以上の炭化水素を意味する。得られたFTオフガスの温度は45℃、圧力は2.75MPaG、流量は1000kmol/h(=15284kg/h)だった。炭素数が5以上の重質炭化水素の含有量は4.32wt%だった。
実施例1で得たFTオフガスを蒸留塔に導入して、塔頂から回収される燃料ガスと塔底から回収される液体状の成分とに分離した(図2)。FTオフガスの塔頂での圧力は2.65MPaG、塔底での温度は198℃、塔頂での温度は-37℃だった。その後、塔頂から得られた燃料ガスに含まれる炭素数が5以上の重質炭化水素の含有量を測定した。
実施例1で得たFTオフガスと軽油に相当する吸収油とを、FTオフガスの圧力2.7MPaG、温度48℃の条件下で単段で直接接触させ、吸収油中に吸収された重質炭化水素を回収した(図3)。用いた吸収油の蒸留性状を表2に示す。また、吸収油の流量は10000kg/hとした。その後、燃料ガスに含まれる、吸収油に吸収されなかった炭素数が5以上の重質炭化水素の含有量を測定した。
実施例3において、さらに吸収油と接触させる際の温度を10℃に冷却し、重質炭化水素を回収した(図4)。吸収油の流量は10000kg/hとした。その後、燃料ガスに含まれる、吸収油に吸収されなかった炭素数が5以上の重質炭化水素の含有量を測定した。
実施例3において、FTオフガスと吸収油とを8段の吸収塔を用いて接触させ、重質炭化水素を回収した(図5)。FTオフガスの圧力は塔頂で2.65MPaG、温度は塔底で49℃、塔頂で50℃だった。また、吸収油の流量は10000kg/hとした。その後、燃料ガスに含まれる、吸収油に吸収されなかった炭素数が5以上の重質炭化水素の含有量を測定した。
実施例3~5において、用いる吸収液の流量を2倍の20000kg/hにした以外は同条件で実験を行い、それぞれ実施例6~8とした。
Claims (8)
- メタンを主成分とする天然ガスとスチーム及び/又は炭酸ガスとを、改質触媒を充填して加熱した管式リフォーマーを通して反応させることにより、水素及び一酸化炭素を主成分とする合成ガスを製造する合成ガス製造工程、
該合成ガス製造工程で製造された合成ガスをフィッシャー・トロプシュ合成反応させた後、ガス状生成物及び未反応合成ガスからなるFTオフガスを分離することにより、フィッシャー・トロプシュ油を製造するフィッシャー・トロプシュ合成工程、並びに
該フィッシャー・トロプシュ油を水素化精製又は水素化分解処理することにより各種炭化水素油を製造するアップグレーディング工程からなり、さらに
該FTオフガスを管式リフォーマーの燃料としてリサイクルする、天然ガスから各種炭化水素油を製造する方法において、
リサイクルする前に該FTオフガスに含まれる重質炭化水素を除去することを特徴とする方法。 - 前記重質炭化水素は炭素数が5以上の炭化水素である、請求項1に記載の方法。
- 前記FTオフガスを吸収油と直接接触させることにより重質炭化水素を除去することを特徴とする、請求項1又は2に記載の方法。
- 前記吸収油は灯油又は軽油である、請求項3に記載の方法。
- 前記FTオフガスを蒸留することにより重質炭化水素を除去することを特徴とする、請求項1又は2に記載の方法。
- 前記FTオフガスを冷却することにより重質炭化水素を除去することを特徴とする、請求項1~4のいずれか1項に記載の方法。
- 吸着剤によりFTオフガスから重質炭化水素を除去することを特徴とする、請求項1又は2に記載の方法。
- 前記吸着剤は活性炭である、請求項7に記載の方法。
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US14/008,355 US20140021094A1 (en) | 2011-03-31 | 2011-03-31 | Method of removing heavy hydrocarbons |
BR112013025178-6A BR112013025178A2 (pt) | 2011-03-31 | 2012-03-22 | método de remoção de hidrocarbonetos pesados |
AP2013007175A AP2013007175A0 (en) | 2011-03-31 | 2012-03-22 | Method of removing heavy hydrocarbons |
CN201280015603.8A CN103492532A (zh) | 2011-03-31 | 2012-03-22 | 重质烃的除去方法 |
EA201391432A EA025037B1 (ru) | 2011-03-31 | 2012-03-22 | Способ получения углеводородных масел |
CA2831552A CA2831552C (en) | 2011-03-31 | 2012-03-22 | Method of removing heavy hydrocarbons |
AU2012235394A AU2012235394B2 (en) | 2011-03-31 | 2012-03-22 | Method of removing heavy hydrocarbons |
EP12764763.4A EP2692833A4 (en) | 2011-03-31 | 2012-03-22 | METHOD FOR REMOVING HEAVY HYDROCARBONS |
ZA2013/07219A ZA201307219B (en) | 2011-03-31 | 2013-09-26 | Method of removing heavy hydrocarbons |
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