CN101432393A - Method for start-up of liquid fuel synthesis system, and liquid fuel synthesis system - Google Patents
Method for start-up of liquid fuel synthesis system, and liquid fuel synthesis system Download PDFInfo
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- CN101432393A CN101432393A CNA2007800156639A CN200780015663A CN101432393A CN 101432393 A CN101432393 A CN 101432393A CN A2007800156639 A CNA2007800156639 A CN A2007800156639A CN 200780015663 A CN200780015663 A CN 200780015663A CN 101432393 A CN101432393 A CN 101432393A
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- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
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- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
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- 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
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- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/24—Starting-up hydrotreatment operations
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- C01B2203/0465—Composition of the impurity
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Abstract
Disclosed is a liquid fuel synthesis system which comprises: a reformer (12) for reforming a hydrocarbon raw material to produce a synthetic gas composed mainly of a carbon monoxide gas and a hydrogen gas; a bubble column reactor (30) for synthesizing a liquid hydrocarbon from the carbon monoxide gas and the hydrogen gas contained in the synthetic gas produced in the reformer (12); hydrogen-utilizing reactors (10, 50, 52, 54) for conducting a given reaction by utilizing the hydrogen gas contained in the synthetic gas produced in the reformer (12); a hydrogen-separation unit (26) for separating a part of the hydrogen gas contained in the synthetic gas produced in the reformer (12); and a hydrogen storage unit (80) for storing the hydrogen gas separated by the hydrogen-separation unit (26). Upon starting up the system, the hydrogen gas stored in the hydrogen storage unit (80) is supplied into the hydrogen-utilizing reactors (10, 50, 52, 54).
Description
Technical field
The present invention relates to starting method, and the liquid fuel synthesis system of liquid fuel synthesis system.
The application advocates right of priority 2006-96015 number for the Japan's patent application in application on March 30th, 2006, quotes its content here.
Background technology
In recent years, as from one of method of Sweet natural gas synthetic liquid fuel, developed GTL (Gas ToLiquid: liquid fuel is synthetic) technology.This technology is by Sweet natural gas being reformed, being generated with CO (carbon monoxide converter) gas (CO) and hydrogen (H
2) be the synthetic gas of principal constituent, with this synthetic gas as unstripped gas, by F-T synthesis reaction (below, be called " FT building-up reactions ") the synthetic fluid hydrocarbon polymer, by this liquid hydrocarbon being carried out hydrogenation and refining, make liquid fuel goods such as petroleum naphtha (raw gasline), lam-oil, light oil, wax again.
In the liquid fuel synthesis system of in the past employing GTL technology, for make, refining synthetic gas, need the oxygen device or remove the equipment of carbonic anhydride, and in order to obtain being fit to the H of FT building-up reactions
2/ CO ratio needs the hydrogen concentration setting device.In addition, in the liquid fuel synthesis system of the GTL technology that adopts present inventors to develop, directly utilize the Sweet natural gas that contains carbonic anhydride as raw material, owing to can obtain being fit to the composition (H of FT building-up reactions by primary first-order equation by utilizing the carbonic anhydride reforming process
2/ CO ratio) therefore synthetic gas can not need the hydrogen concentration setting device.
; the reformer that adopts the liquid fuel synthesis system of above-mentioned GTL technology in the past to possess the reformation hydrocarbon material to generate CO (carbon monoxide converter) gas and hydrogen, the various reaction units that utilize hydrogen (for example, be used for the desulphurization reactor of selexol process or be used for the synthetic liquid hydrocarbon is carried out the hydrogenator etc. of hydrogenation) that need utilize hydrogen that this reformer generates.But, in liquid fuel synthesis system in the past, from reformer starting up to generating CO (carbon monoxide converter) gas and hydrogen, the above-mentioned reaction unit that utilizes hydrogen of fail to start, thereby the starting of the above-mentioned reaction unit that utilizes hydrogen is slow.Therefore, the entire system entry into service, begin to produce the liquid hydrocarbon goods and need spended time, become the reason that production efficiency descends.
Summary of the invention
The present invention finishes in view of the above problems, and its purpose is to provide a kind of starting method that makes the liquid fuel synthesis system that the reaction unit that utilizes hydrogen starts rapidly, can enhance productivity, and liquid fuel synthesis system.
The starting method of liquid fuel synthesis system of the present invention is the starting method of following liquid fuel synthesis system, and this liquid fuel synthesis system possesses to be reformed and generate with CO (carbon monoxide converter) gas and hydrogen and be the reformer of the synthetic gas of principal constituent, come the reactor of synthetic fluid hydrocarbon polymer and utilized the reaction unit that utilizes hydrogen that contained hydrogen carries out the regulation reaction in the synthetic gas generate in described reformer by CO (carbon monoxide converter) gas contained in the described synthetic gas and hydrogen hydrocarbon material; When the normal operation of described liquid fuel synthesis system, the part of hydrogen contained in the synthetic gas that generates in described reformer is separated and stored, when the starting of described liquid fuel synthesis system, the hydrogen that is stored in the described hydrogen-storing device is supplied to the described reaction unit that utilizes hydrogen.
Starting method according to liquid fuel synthesis system of the present invention, because when the starting of the reaction unit that utilizes hydrogen, the hydrogen of storing in advance during with the normal operation of liquid fuel within synthesis system supplies to the reaction unit that utilizes hydrogen, therefore can begin to utilize the regulation reaction of hydrogen in this utilizes the reaction unit of hydrogen immediately.Thereby, can make and utilize the reaction unit of hydrogen to start rapidly before the reformer hydrogen supply, therefore can improve the production efficiency of liquid fuel synthesis system.
In the starting method of liquid fuel synthesis system of the present invention, the described reaction unit that utilizes hydrogen also can comprise synthetic liquid hydrocarbon in described reactor is carried out the hydrogenator of hydrogenation and the hydrocarbon material that supplies to described reformer carried out any at least in the desulphurization reactor of hydro-desulfurization.
In the starting method of liquid fuel synthesis system of the present invention, described hydrogen also can separate by any at least method in pressure variation absorption method, hydrogen storage alloy absorption method and the membrane separation process.
In the starting method of liquid fuel synthesis system of the present invention, described reactor also can be the tower suspension bed formula of bubble reactor (being also referred to as " the tower slurry bubble bed formula of bubble reactor ").
Liquid fuel synthesis system of the present invention possesses: reformer, and it is reformed to hydrocarbon material, and generating with CO (carbon monoxide converter) gas and hydrogen is the synthetic gas of principal constituent; Reactor, it comes the synthetic fluid hydrocarbon polymer by CO (carbon monoxide converter) gas contained in the described synthetic gas and hydrogen; Utilize the reaction unit of hydrogen, it utilizes, and contained hydrogen carries out the regulation reaction in the synthetic gas that generates in described reformer; The hydrogen tripping device, its part to hydrogen contained in the synthetic gas that generates in described reformer is separated; Hydrogen-storing device, it is stored by described hydrogen tripping device and separates the hydrogen that obtains; Controlling organization, it supplies to the described reaction unit that utilizes hydrogen with the hydrogen that is stored in the described hydrogen-storing device when the starting of described liquid fuel synthesis system.
In liquid fuel synthesis system of the present invention, the above-mentioned reaction unit that utilizes hydrogen also can comprise synthetic liquid hydrocarbon in described reactor is carried out the hydrogenator of hydrogenation and the hydrocarbon material that supplies to described reformer carried out any at least in the desulphurization reactor of hydro-desulfurization.
In liquid fuel synthesis system of the present invention, above-mentioned hydrogen tripping device also can be by any at least method separating hydrogen gas in pressure variation absorption method, hydrogen storage alloy absorption method and the membrane separation process.
In liquid fuel synthesis system of the present invention, above-mentioned reactor is the tower suspension bed formula of a bubble reactor.
According to the present invention, the reaction unit that utilizes hydrogen that is located in the liquid fuel synthesis system is started rapidly, can improve the production efficiency of liquid fuel.
Description of drawings
Fig. 1 is the schematic drawing that the integral body of the liquid fuel synthesis system of expression embodiments of the present invention constitutes.
Fig. 2 is the figure on opportunity of the starting method in the past of express liquid fuel synthesis system.
Fig. 3 is the opportunity figure of starting method of the liquid fuel synthesis system of this embodiment of expression.
Fig. 4 is the module map of configuration example of the hydrogen-storing device in the liquid fuel synthesis system of this embodiment of expression.
Fig. 5 is the module map of another configuration example of the hydrogen-storing device in the liquid fuel synthesis system of this embodiment of expression.
Nomenclature
1 ... liquid fuel synthesis system, 3 ... the synthetic gas generation unit, 5 ... the FT synthesis unit, 7 ... the goods refined unit, 10 ... desulphurization reactor, 12 ... reformer, 14 ... the heat extraction boiler, 16,18 ... gas-liquid separator, 20 ... the decarbonate device, 22 ... the absorption tower, 24 ... regenerator column, 26 ... the hydrogen tripping device, 30 ... the bubble tower reactor, 32 ... heat pipe, 34,38 ... gas-liquid separator, 36 ... separator, 40 ... the 1st rectifying tower, 50 ... the wax slop hydrocracking reactor, 52 ... lam-oil and light oil distillate hydrofining reactor, 54 ... the naphtha fraction hydrofining reactor, 56,58,60 ... gas-liquid separator, 70 ... the 2nd rectifying tower, 72 ... the petroleum naphtha stabilizer, 80 ... hydrogen-storing device, 81,101 ... hold-up vessel, 82,83,104 ... hydrogen compressor, 84,105 ... controller, 86,87,106,107 ... valve, 91,92,93,94,95 ... pipe arrangement, 102 ... liquefying plant, 103 ... gasification installation
Embodiment
Below, preferred embodiment be described in detail of the present invention with reference to accompanying drawing.Have again, in this specification sheets and accompanying drawing, use identical symbol for having the integrant that identical function in fact constitutes, and the repetitive description thereof will be omitted.
At first, with reference to Fig. 1, the integral body of the liquid fuel synthesis system 1 of employing GTL (the Gas To Liquid) technology of embodiments of the present invention is constituted and work describes.Fig. 1 is the schematic drawing that the integral body of the liquid fuel synthesis system 1 of expression present embodiment constitutes.
As shown in Figure 1, the liquid fuel synthesis system 1 of present embodiment is to carry out the suite of equipment (plant) that hydrocarbon materials such as Sweet natural gas is converted to the GTL technology of liquid fuel.This liquid fuel synthesis system 1 is made of synthetic gas generation unit 3, FT synthesis unit 5 and goods refined unit 7.3 pairs of hydrocarbon materials of synthetic gas generation unit are that Sweet natural gas is reformed, and generate the synthetic gas that contains CO (carbon monoxide converter) gas and hydrogen.FT synthesis unit 5 is by F-T synthesis reaction (below, be called " FT building-up reactions "), from the synthesis gas producing fluid body hydrocarbon polymer that generates.7 pairs of liquid hydrocarbons that generate by the FT building-up reactions of goods refined unit carry out hydrofining, make liquid fuel (petroleum naphtha, lam-oil, light oil, wax etc.).Below, above-mentioned each unitary integrant is described.
At first, synthetic gas generation unit 3 is described.Synthetic gas generation unit 3 for example mainly possesses: desulphurization reactor 10, reformer 12, heat extraction boiler 14, gas-liquid separator 16 and 18, decarbonate device 20, hydrogen tripping device 26.Desulphurization reactor 10 is made of hydro-desulfurization device etc., and being used for from raw material is that Sweet natural gas removes the desulfuration composition.12 pairs of Sweet natural gases of supplying with from desulphurization reactor 10 of reformer are reformed, and generate and contain CO (carbon monoxide converter) gas (CO) and hydrogen (H
2) as the synthetic gas of principal constituent.Heat extraction boiler 14 is recovered in the heat extraction of the synthetic gas that generates in the reformer 12, produces high pressure steam.Gas-liquid separator 16 will be by becoming gas (high pressure steam) and liquid with the heated water sepn of the heat exchange of synthetic gas in heat extraction boiler 14.Gas-liquid separator 18 is removed condensation portion from the synthetic gas that is cooled at heat extraction boiler 14, gas is partly supplied to decarbonate device 20.Decarbonate device 20 has and adopts absorption liquid to remove the absorption tower 22 of carbonic anhydride and carbonic anhydride is distributed from the synthetic gas of being supplied with by gas-liquid separator 18 to carry out regenerated regenerator column 24.Hydrogen tripping device 26 separates a part of hydrogen contained in this synthetic gas from the synthetic gas that has been separated carbonic anhydride by decarbonate device 20.But above-mentioned decarbonate device 20 does not according to circumstances need to be provided with sometimes.
Wherein, reformer 12 for example by the water vapour carbonic anhydride reforming process with following chemical equation (1), (2) expression, adopts carbonic acid gas and water vapour that Sweet natural gas is reformed, and generating with CO (carbon monoxide converter) gas and hydrogen is the pyritous synthetic gas of principal constituent.Have again, these reformer 12 used reforming process are not limited to the example of above-mentioned water vapour carbonic anhydride reforming process, for example, also can utilize the steam reforming method, adopted the partial oxidation reforming process (POX) of oxygen, self-heating recapitalization method (ATR) that partial oxidation reforming process and steam reforming method are combined, carbonic anhydride reforming process etc.
CH
4+H
2O→CO+3H
2……(1)
CH
4+CO
2→2CO+2H
2……(2)
In addition, hydrogen tripping device 26 is arranged on the branch line of going out from the main pipe arrangement branch that connects decarbonate device 20 or gas-liquid separator 18 and bubble tower reactor 30.This hydrogen tripping device 26 is for example by utilizing pressure difference to carry out formations such as the hydrogen PSA of the absorption and the desorb of hydrogen (Pressure Swing Adsorption: pressure variation is adsorbed) device.This hydrogen PSA device has sorbent material (zeolite is sorbent material, gac, aluminum oxide, silica gel etc.) in a plurality of adsorption towers (not shown) of configuration side by side, pressurization by repeating hydrogen successively at each adsorption tower, absorption, desorb (decompression), each operation that purifies can will supply to reactor continuously from the high hydrogen of the isolating purity of synthetic gas (for example about 99.999%).
Have again,, be not limited to the example of the such pressure variation absorption method of above-mentioned hydrogen PSA device, for example, also can adopt hydrogen storage alloy absorption method, membrane separation process or their combination etc. as the Hydrogen Separation method in the hydrogen tripping device 26.
The hydrogen storage alloy absorption method for example is to adopt to have hydrogen storage alloy (TiFe, the LaNi that adsorbs/emit the character of hydrogen by cooling
5, TiFe
0.7-0.9, Mn
0.3-0.1, or TiMn
1.5Deng) method of coming separating hydrogen gas.A plurality of adsorption towers that contain hydrogen storage alloy are set, and in each adsorption tower, the utilization of cooling off the absorption of carrying out hydrogen and hydrogen storage alloy by the utilization that alternately repeats hydrogen storage alloy is heated and is carried out emitting of hydrogen, can separate and reclaim the hydrogen in the synthetic gas.
In addition, membrane separation process is the raw-material films of polymer such as employing aromatic polyimide, the method for separating the good hydrogen of membrane perviousness from gas mixture.This membrane separation process is not owing to follow phase change, and the required energy that therefore turns round is little, and the furnace lining expense is low.In addition, membrane separation unit simple in structure, compact, so equipment cost is low, the required area of equipment is also little.And separatory membrane does not have drive unit, and the steady running scope is wide, therefore has the advantage of the maintenance management of being easy to.
Then, FT synthesis unit 5 is described.FT synthesis unit 5 for example mainly possesses bubble tower reactor 30, gas-liquid separator 34, separator 36, gas-liquid separator 38 and the 1st rectifying tower 40.Bubble tower reactor 30 makes in above-mentioned synthetic gas generation unit 3 synthetic gas that generates, is that the FT building-up reactions takes place for CO (carbon monoxide converter) gas and hydrogen, generates liquid hydrocarbon.Circulation and heated water sepn become water vapour (middle pressure steam) and liquid in the heat pipe 32 that gas-liquid separator 34 will set in bubble tower reactor 30.Separator 36 is connected the central part of bubble tower reactor 30, and catalyzer and liquid hydrocarbon product are carried out separating treatment.Gas-liquid separator 38 is connected the top of bubble tower reactor 30, and unreacted synthetic gas and gaseous hydrocarbons product are carried out cooling process.40 pairs of liquid hydrocarbons of supplying with via separator 36, gas-liquid separator 38 from bubble tower reactor 30 of the 1st rectifying tower distill, and separate, are refined into each goods cut according to boiling point.
Wherein, bubble tower reactor 30 is examples that synthetic gas synthesized the reactor of liquid hydrocarbon, has as passing through the FT building-up reactions from the synthetic function with reactor of the FT of synthetic gas synthetic fluid hydrocarbon polymer.This bubble tower reactor 30 for example is made of the tower suspension bed formula of the bubble reactor that leaves the slurries that comprise catalyzer and medium oil in tower internal tank storage.This bubble tower reactor 30 passes through the FT building-up reactions by synthesis gas producing fluid body hydrocarbon polymer.At length say, in this bubble tower reactor 30, to be synthetic gas become bubble and supply with from the breaker plate of the bottom of bubble tower reactor 30 unstripped gas, in the slurries that comprise catalyzer and medium oil, pass through, in outstanding turbid state shown in following chemical equation (3), hydrogen and CO (carbon monoxide converter) gas generation building-up reactions.
2nH
2+nCO→(—CH
2—)
n+nH
2O……(3)
Because this FT building-up reactions is thermopositive reaction, therefore bubble tower reactor 30 is for having set the heat exchanger-type of heat pipe 32 in inside, for example supply with water (BFW:Boiler Feed Water, oiler feed) is used as refrigerant, can reclaims the reaction heat of above-mentioned FT building-up reactions as middle pressure steam by the heat exchange of slurries and water.
At last, goods refined unit 7 is described.Goods refined unit 7 for example possesses: wax slop hydrocracking reactor 50, lam-oil and light oil distillate hydrofining reactor 52, naphtha fraction hydrofining reactor 54, gas-liquid separator the 56,58,60, the 2nd rectifying tower 70, petroleum naphtha stabilizer 72.Wax slop hydrocracking reactor 50 is connected the bottom of the 1st rectifying tower 40.Lam-oil and light oil distillate hydrofining reactor 52 are connected the central part of the 1st rectifying tower 40.Naphtha fraction hydrofining reactor 54 is connected the top of the 1st rectifying tower 40.Gas-liquid separator 56,58,60 is provided with accordingly with these hydrogenators 50,52,54 respectively.The 2nd rectifying tower 70 separates the liquid hydrocarbon of supplying with from gas-liquid separator 56,58 according to boiling point and makes with extra care.72 pairs of liquid hydrocarbons from the naphtha fraction of gas-liquid separator 60 and 70 supplies of the 2nd rectifying tower of petroleum naphtha stabilizer carry out rectifying, and the composition lighter than butane arranged to tail gas (exhaust) side, and the Separation and Recovery carbon number is C
5Above composition is as the petroleum naphtha of goods.
Then, the operation (GTL technology) of the liquid fuel synthesis system 1 by above-mentioned formation from the Sweet natural gas synthetic liquid fuel described.
From outside Sweet natural gas supply source (not shown) such as natural-gas field or Sweet natural gas suite of equipment, (principal constituent is CH to supply with Sweet natural gas as hydrocarbon material to liquid fuel synthesis system 1
4).3 pairs of these Sweet natural gases of above-mentioned synthetic gas generation unit are reformed, and make synthetic gas (is the gas mixture of principal constituent with CO (carbon monoxide converter) gas and hydrogen).
Specifically be, at first, with above-mentioned Sweet natural gas with separate the hydrogen that obtains by hydrogen tripping device 26 and together supply to desulphurization reactor 10.Desulphurization reactor 10 adopts this hydrogen that sulphur composition contained in the Sweet natural gas is carried out hydro-desulfurization by for example ZnO catalyst.With selexol process, can prevent that the activity of such catalysts of using in reformer 12 and the bubble tower reactor 30 etc. from reducing because of sulphur by so in advance.
By the Sweet natural gas (also can contain carbonic acid gas) of so desulfurization with the carbonic acid gas (CO that supplies with from carbonic acid gas supply source (not shown)
2) gas and after the water vapour that heat extraction boiler 14 produces mixes, be fed into reformer 12.Reformer 12 for example utilizes above-mentioned water vapour carbonic anhydride reforming process, adopts carbonic acid gas and water vapour that Sweet natural gas is reformed, and generating with CO (carbon monoxide converter) gas and hydrogen is the pyritous synthetic gas of principal constituent.At this moment, supply with fuel gas and the air that burner that reformer 12 for example possesses is used to reformer 12, by the combustion heat of the fuel gas in this burner, supplying with thermo-negative reaction is the required reaction heat of above-mentioned water vapour carbonic anhydride reforming reaction.
The pyritous synthetic gas (for example, 900 ℃, 2.0MPaG) that so generates at reformer 12 is supplied to heat extraction boiler 14, and by with the heat exchange of the water of circulation in heat extraction boiler 14 this synthetic gas being cooled off (for example 400 ℃), heat extraction is recovered.At this moment, the water supply that will be synthesized the gas heating in heat extraction boiler 14 is to gas-liquid separator 16, from this gas-liquid separator 16 gas part (for example 3.4～10.0MPaG) is supplied to reformer 12 or other external device (ED), the water of liquid portion is turned back to heat extraction boiler 14 with high pressure steam.
On the other hand, the synthetic gas that is cooled in heat extraction boiler 14 after the phlegma part is removed in separation in gas-liquid separator 18, supplies to the absorption tower 22 or the bubble tower reactor 30 of decarbonate device 20.Absorption tower 22 is removed carbonic anhydride by absorbing in the absorption liquid of storage by contained carbonic anhydride from this synthetic gas in synthetic gas.The absorption liquid that contains carbonic anhydride in this absorption tower 22 is imported in the regenerator column 24, the absorption liquid that for example contains this carbonic anhydride with steam heating, carry out stripping and handle, the carbonic anhydride that discharges is sent to the reformer 12 from regenerator column 24, be used in above-mentioned reforming reaction again.
So, the synthetic gas that will generate in synthetic gas generation unit 3 supplies to the bubble tower reactor 30 of above-mentioned FT synthesis unit 5.At this moment, the ratio of components that supplies to the synthetic gas of bubble tower reactor 30 is adjusted to ratio of components (for example, the H that is fit to the FT building-up reactions
2: CO=2: 1 (mol ratio)).Have again, supply to the synthetic gas of bubble tower reactor 30, boosted by the compressor (not shown) that is located on the pipe arrangement that connects decarbonate device 20 and bubble tower reactor 30 to the pressure (for example 3.6MPaG) that is fit to the FT building-up reactions.
In addition, will also supply to hydrogen tripping device 26 by the part that above-mentioned decarbonate device 20 has separated the synthetic gas of carbonic anhydride.Hydrogen tripping device 26 is absorption, the desorb (hydrogen PSA) by utilizing pressure difference as mentioned above, is separated in hydrogen contained in the synthetic gas.The hydrogen that this is separated supplies to continuously via compressor (not shown) from gas-holder (not shown) etc. and utilizes hydrogen to carry out the various reaction units (for example, desulphurization reactor 10, wax slop hydrocracking reactor 50, lam-oil and light oil distillate hydrofining reactor 52, naphtha fraction hydrofining reactor 54 etc.) that utilize hydrogen of regulation reaction in the liquid fuel within synthesis system 1.
Then, the synthetic gas of above-mentioned FT synthesis unit 5 from being generated by above-mentioned synthetic gas generation unit 3 is by FT building-up reactions synthetic fluid hydrocarbon polymer.
Specifically be, flow into the synthetic gas that generates by above-mentioned synthetic gas generation unit 3 from the bottom of bubble tower reactor 30, rise in the catalyst slurry in bubble tower reactor 30 is stayed in storage.At this moment, in bubble tower reactor 30, by above-mentioned FT building-up reactions, carbon monoxide and hydrogen contained in this synthetic gas react, and generate hydrocarbon polymer.And, when this building-up reactions, in the heat pipe 32 of bubble tower reactor 30, flow by making water, remove the reaction heat of FT building-up reactions, make heated aqueous vaporization become water vapour by this heat exchange.This water vapour water that forms that liquefies in gas-liquid separator 34 turns back to heat pipe 32, and the gas part (for example 1.0～2.5MPaG) is fed into external device (ED) as middle pressure steam.
Thus, the central part from bubble tower reactor 30 takes out synthetic liquid hydrocarbon bubble tower reactor 30, importing separator 36.Separator 36 separates the catalyzer (solid part) in the slurries that take out with the liquid portion that contains the liquid hydrocarbon product.The part of isolated catalyzer is turned back to bubble tower reactor 30, liquid portion is supplied to the 1st rectifying tower 40.In addition, from the cat head of bubble tower reactor 30, the gas of unreacted synthetic gas and synthetic hydrocarbon polymer is partly imported to gas-liquid separator 38.Gas-liquid separator 38 separates the liquid hydrocarbon of the condensation portion of a part with these gas cooling, imports the 1st rectifying tower 40.On the other hand, for separating the gas part that obtains, with unreacted synthetic gas (CO and H by gas-liquid separator 38
2) put into the bottom of bubble tower reactor 30 again, be used in the FT building-up reactions again, in addition, will be with the few (C of carbon number beyond the goods object
4Below) hydrocarbon gas be that the exhaust (tail gas) of principal constituent imports in the outside combustion equipment (not shown), discharge in atmosphere the burning back.
Then, the liquid hydrocarbon (carbon number is various) that 40 heating of the 1st rectifying tower are supplied with via separator 36, gas-liquid separator 38 from bubble tower reactor 30 as mentioned above, utilize the difference of boiling point to carry out fractionation, separation and purification becomes naphtha fraction (boiling point is less than about 315 ℃ greatly), lam-oil and light oil distillate (boiling point is approximately 315～800 ℃), wax slop (boiling point is approximately higher than 800 ℃ greatly).The liquid hydrocarbon of the wax slop that will take out from the bottom of the 1st rectifying tower 40 (is mainly C
21More than) being transplanted on wax slop hydrocracking reactor 50, the lam-oil that will take out from the central part of the 1st rectifying tower 40 and the liquid hydrocarbon of light oil distillate (are mainly C
11～C
20) being transplanted on lam-oil and light oil distillate hydrofining reactor 52, the liquid hydrocarbon of the naphtha fraction that will take out from the top of the 1st rectifying tower 40 (is mainly C
5～C
10) be transplanted on naphtha fraction hydrofining reactor 54.
Wax slop hydrocracking reactor 50 utilizes the hydrogen of supplying with from above-mentioned hydrogen tripping device 26, will be from the carbon number of the underfeed of the 1st rectifying tower 40 liquid hydrocarbon of many wax slops (be generally C
21More than) hydrocracking, carbon number is reduced to C
20Below.In this hydrocracking reaction, utilize catalyzer and heat, cut off the C-C key of the many hydrocarbon polymers of carbon number, generate the few low-molecular-weight hydrocarbon polymer of carbon number.By this wax slop hydrocracking reactor 50, the product of the liquid hydrocarbon that has contained by hydrocracking is separated into gas and liquid in gas-liquid separator 56, liquid hydrocarbon wherein is shifted into the 2nd rectifying tower 70, and gas part (containing hydrogen) is shifted into lam-oil and light oil distillate hydrofining reactor 52 and naphtha fraction hydrofining reactor 54.
Lam-oil and light oil distillate hydrofining reactor 52 adopts the hydrogen of supplying with via wax slop hydrocracking reactor 50 from hydrogen tripping device 26, is that the moderate lam-oil and the liquid hydrocarbon of light oil distillate (are generally C to the carbon number of supplying with from the central part of the 1st rectifying tower 40
11～C
20) carry out hydrofining.This hydrofining reaction is that the unsaturated link(age) addition hydrogen to the aforesaid liquid hydrocarbon polymer makes it saturated and generate the reaction of straight chain shape saturated hydrocarbon.The result contains by the product of hydrorefined liquid hydrocarbon to be separated into gas and liquid in gas-liquid separator 58, liquid hydrocarbon wherein is shifted into the 2nd rectifying tower 70, and gas part (containing hydrogen) is reused in above-mentioned hydrogenation reaction.
Naphtha fraction hydrofining reactor 54 adopts the hydrogen of supplying with via wax slop hydrocracking reactor 50 from hydrogen tripping device 26, and the liquid hydrocarbon of the few naphtha fraction of the carbon number supplied with from the top of the 1st rectifying tower 40 (is generally C
10Below) carry out hydrofining.The result contains by the product of hydrorefined liquid hydrocarbon to be separated into gas and liquid in gas-liquid separator 60, liquid hydrocarbon wherein is shifted into petroleum naphtha stabilizer 72, and gas part (containing hydrogen) is reused in above-mentioned hydrogenation reaction.
Then, 70 pairs on the 2nd rectifying tower distills from the liquid hydrocarbon that wax slop hydrocracking reactor 50 and lam-oil and light oil distillate hydrofining reactor 52 are supplied with as mentioned above, and it is C that separation and purification becomes carbon number
10Following hydrocarbon polymer (boiling point is less than about 315 ℃ greatly), lam-oil (boiling point is approximately 315～450 ℃), and light oil (boiling point is approximately 450～800 ℃).Take out light oil from the bottom of the 2nd rectifying tower 70, take out lam-oil from central part.On the other hand, the cat head taking-up carbon number from the 2nd rectifying tower 70 is C
10Following hydrocarbon gas supplies to petroleum naphtha stabilizer 72.
And, in petroleum naphtha stabilizer 72, be C to the carbon number supplied with from above-mentioned naphtha fraction hydrofining reactor 54 and the 2nd rectifying tower 70
10Following hydrocarbon polymer distills, and separates and refining petroleum naphtha (C as goods
5～C
10).Thereby, take out highly purified petroleum naphtha from the bottom of petroleum naphtha stabilizer 72.On the other hand, discharge with the carbon number (C below stated number beyond the goods object from the cat head of petroleum naphtha stabilizer 72
4Below) hydrocarbon polymer be the exhaust (tail gas) of principal constituent.This exhaust is imported in the outside combustion equipment (not shown), and discharge in atmosphere the burning back.
More than, the work (GTL technology) of liquid fuel synthesis system 1 is illustrated.According to this GTL technology, can be easily and economically Natural Gas Conversion is become highly purified petroleum naphtha (C
5～C
10: raw gasline), lam-oil (C
11～C
15: kerosene) and light oil (C
16～C
20: gas oil) liquid fuel of cleaning such as.And, in the present embodiment, advantage is: by adopt above-mentioned water vapour carbonic anhydride reforming process in reformer 12, can effectively utilize carbonic acid gas contained in the Sweet natural gas as raw material, and can generate ratio of components (for example, the H of the synthetic gas that is fit to above-mentioned FT building-up reactions expeditiously by 1 secondary response of reformer 12
2: CO=2: 1 (mol ratio)), do not need hydrogen concentration setting device etc.
Then, in the liquid fuel synthesis system 1 of present embodiment, be described in detail to the plenum system that utilizes hydrogen to carry out the reaction unit hydrogen supply that utilizes hydrogen of regulation reaction.
In aforesaid liquid fuel synthesis system 1, its formation is: when running well (when the specified running after system's starting process specified time), in hydrogen tripping device 26, the part of the hydrogen in the synthetic gas that generates in reformer 12 is separated, the hydrogen that this separation is obtained supplies to reaction unit (for example, the desulphurization reactor 10 of synthetic gas generation unit 3 that utilizes hydrogen continuously, and the wax slop hydrocracking reactor 50 of goods refined unit 7, lam-oil and light oil distillate hydrofining reactor 52 and naphtha fraction hydrofining reactor 54 (below be generically and collectively referred to as " hydrogenator 50; 52; 54 ")).
; if only use such hydrogen plenum system; during the starting of liquid fuel within synthesis system 1 (when also comprising the starting of each unit 3,5,7); reformer 12 starting back up to become normal operation, stably generate and supply with synthetic gas before; not to hydrogenator 50,52,54 hydrogen supplies of said products refined unit 7, thereby this hydrogenator 50,52,54 of fail to start.Therefore,, before liquid fuel synthesis system 1 whole entry into service, manufacturing liquid fuel goods, need the suitable time, therefore have the low problem of production efficiency in the past.
For the start delay of the hydrogenator 50,52,54 of this goods refined unit 7, carry out specific description with reference to Fig. 2.As shown in Figure 2, in the past, when starting liquid fuel synthesis system 1, at first, the reformer 12 of starting synthetic gas generation unit 3, the formation reaction of beginning synthetic gas.To this reformer 12 reach normal operation, in the time of can stably supplying with synthetic gas, the time counting from starting for example has been the 4th day.In addition, for FT synthesis unit 5, during from the starting of synthetic gas generation unit 3, for example after 1 day, make its starting, if carry out the adjustment of device and the preparation of FT building-up reactions, then stably carry out the FT building-up reactions from beginning in the 4th day identical with the date of synthetic gas generation unit 3 specified runnings.
; for goods refined unit 7; if not supply to hydrogenator 50,52,54 backs (after above-mentioned the 4th day) from the hydrogen that will reformer 12, generate, then can not make hydrogenator 50,52,54 startings, can not begin the preparation of catalyst reduction or hydrogenation reaction.Therefore, the time that goods refined unit 7 can stably carry out hydrogenation, refining reaction has been for example to count during from the starting of synthetic gas generation unit 3 by the 8th day, needs the long starting time.Thereby, whole entry into service fully of liquid fuel synthesis system 1 and the time that can stably make the liquid fuel goods are to start at for example the 8th day (the specified running of synthetic gas generation unit 3 begin after the 4th day) during from the starting of synthetic gas generation unit 3, very evening, there is the low problem of production efficiency.
And, during from the starting of synthetic gas generation unit 3, at the 4th day to the 7th day, FT synthesis unit 5 runs well, but because goods refined unit 7 do not run well, therefore also exist need be used to store the liquid hydrocarbon that generates by the FT building-up reactions (hydrogenation and refining before work in-process) work in-process store problem with jar (not shown).
Therefore, for addressing these problems, in the liquid fuel synthesis system 1 of present embodiment, as shown in Figure 1, be provided for storing hydrogen-storing device 80, the hydrogen that is stored in this hydrogen-storing device 80 can be supplied to the desulphurization reactor 10 of above-mentioned synthetic gas generation unit 3 or the hydrogenator 50,52,54 of goods refined unit 7 etc. by hydrogen tripping device 26 hydrogen of Separation and Recovery from synthetic gas.That is to say, utilize the reaction unit of hydrogen for desulphurization reactor 10 or hydrogenator 50,52,54 etc., with plenum system from above-mentioned hydrogen tripping device 26 direct hydrogen supplies be provided with dividually with from the hydrogen temporary storage of hydrogen tripping device 26 hydrogen-storing device 80 and the plenum system of supplying with indirectly.
In such formation, during the normal operation of liquid fuel within synthesis system 1, will not supply to above-mentioned desulphurization reactor 10 or hydrogenator 50,52,54 etc. and utilize the reaction unit of hydrogen, and the part of this hydrogen will be stored in the hydrogen-storing device 80 by hydrogen tripping device 26 isolating whole hydrogen from synthetic gas.Then, when the restarting of thereafter liquid fuel synthesis system 1 etc. in, restarting hydrogenator at 50,52,54 o'clock, the hydrogen that is stored in the hydrogen-storing device 80 can be supplied to hydrogenator 50,52,54 or desulphurization reactor 10 etc. immediately.Therefore, can be in reformer 12 starting, stably before the hydrogen supply, start the reaction unit that above-mentioned hydrogenator 50,52,54 or desulphurization reactor 10 etc. utilize hydrogen from this reformer 12 rapidly.
Specifically be as shown in Figure 3, when restarting the liquid fuel synthesis system 1 of present embodiment, at first, will to be stored in the hydrogenator 50,52,54 that hydrogen in the hydrogen-storing device 80 supplies to goods refined unit 7.Thereby, can make hydrogenator 50,52,54 startings, the preparation of beginning catalytic reduction or hydrogenation reaction at the prestart of reformer 12.Then, after beginning 1 day from the starting of hydrogenator 50,52,54, starting synthetic gas generation unit 3, supply with the hydrogen that is stored in the hydrogen-storing device 80 to desulphurization reactor 10, start reformer 12 simultaneously, start, and then, after it is 1 day, make 5 startings of FT synthesis unit, carry out the preparation of device adjustment and FT building-up reactions.Thus, can from the starting of above-mentioned hydrogenator 50,52,54 time, start at for example at the 5th day, the reformer 12 that can run well is stably supplied with synthetic gas, can stably generate liquid hydrocarbon by the FT building-up reactions in bubble tower reactor 30 simultaneously.And, (the 5th day) at this moment, in goods refined unit 7, because the preparation work of hydrogenator 50,52,54 etc. finishes, therefore goods refined unit 7 can stably carry out can beginning the manufacturing of liquid fuel goods from the hydrogenation reaction (reduction reaction/hydrocracking reaction) and the refining reaction of the liquid hydrocarbon of FT synthesis unit 5 supplies.
Like this, in the present embodiment, during the restarting of liquid fuel within synthesis system 1, supply to hydrogenator 50,52,54 or desulphurization reactor 10 by the hydrogen that will be stored in the hydrogen-storing device 80, can shorten the starting time of entire system, begin to make the liquid fuel goods ahead of time, thereby can enhance productivity.
Here, with reference to Fig. 4 and Fig. 5, the configuration example of the hydrogen-storing device 80 in the liquid fuel synthesis system 1 of present embodiment is described in detail.Fig. 4 and Fig. 5 are respectively the module map of configuration example of the hydrogen-storing device 80 in the liquid fuel synthesis system 1 of expression present embodiment.Have again, in Fig. 4 and Fig. 5, for convenience of explanation, only illustrate the major portion in the integrant of liquid fuel synthesis system 1,, omitted diagram for a part of integrant.
As Fig. 4 and shown in Figure 5, in the liquid fuel within synthesis system 1, connect hydrogen tripping device 26 and hydrogen-storing device 80 by pipe arrangement 91, connect this hydrogen-storing device 80 and desulphurization reactor 10 and hydrogenator 50,52,54 by pipe arrangement 92,93 respectively.
At first, the hydrogen-storing device 80 to the example of Fig. 4 is described in detail.As shown in Figure 4, hydrogen-storing device 80 possesses: the hold-up vessel 81 that is made of pressure vessels such as for example spherical storage tanks; Be connected and be connected the hydrogen compressor 82 of the inlet side of hold-up vessel 81 with pipe arrangement 91 from above-mentioned hydrogen tripping device 26; Be connected the outlet side of hold-up vessel 81 and be connected to hydrogen compressor 83 on desulphurization reactor 10 and the hydrogenator 50,52,54 via above-mentioned pipe arrangement 92,93; Be used to control the controller 84 of the each several part of hydrogen-storing device 80.Have, controller 84 is examples of controlling organization of the work (for example, the supply work of the storage work of hydrogen or hydrogen that supply with to store to the reaction unit that utilizes hydrogen etc.) of control hydrogen-storing device 80 again.
Work to the hydrogen-storing device 80 of Fig. 4 of formation like this describes below.When the normal operation of aforesaid liquid fuel synthesis system 1,, supply with desulphurization reactor 10 or hydrogenator 50,52,54 by pipe arrangement 94,95 by the part of hydrogen tripping device 26 separating and reclaiming hydrogen from the synthetic gas that reformer 12, generates.When this runs well, to controller 84 input of hydrogen-storing device 80 for example based on the storage indicator signal of operator's input or from the storage indicator signal of the controller (not shown) of liquid fuel synthesis system 1.So controller 84 carries out following control in order to store hydrogen in hold-up vessel 81: make hydrogen compressor 82 work, open the valve 86 of the inlet side of hold-up vessel 81, close the valve 87 of outlet side simultaneously.Thus, an one of the hydrogen that will discharge from hydrogen tripping device 26 supplies to hydrogen compressor 82 by pipe arrangement 91, and the hydrogen of 82 pairs of supplies of hydrogen compressor compresses, and is stored in the hold-up vessel 81 with the storage pressure (for example 3MPaG) of regulation.Then, in the moment of the hydrogen of having stored q.s, controller 84 stops the work of hydrogen compressor 82, closes the valve 86 of the inlet side of hold-up vessel 81, finishes to store action.
On the other hand, when the starting of aforesaid liquid fuel synthesis system 1,, for example import based on the supply indicator signal of operator input or from the supply indicator signal of the controller (not shown) of liquid fuel synthesis system 1 to the controller 84 of hydrogen-storing device 80.So controller 84 to be stored in the hydrogen in the hold-up vessel 81 and to carry out following control in order to supply with as mentioned above: make hydrogen compressor 83 runnings,, open the valve 87 of outlet side with the state of the valve 86 of the inlet side of closing hold-up vessel 81.Thus, the hydrogen that is stored in the hold-up vessel 81 is boosted to the specified pressure (for example 3.6MPaG) that is fit to bubble tower reactor 30 by hydrogen compressor 83, and the hydrogen that this is boosted supplies to desulphurization reactor 10 and hydrogenator 50,52,54 by pipe arrangement 92,93.Like this, in the example of Fig. 4, can adopt the better simply hydrogen-storing device 80 of device constituent ratio, during the starting of liquid fuel within synthesis system 1, the hydrogen that is stored in the hold-up vessel 81 be supplied to required place immediately.
Then, the hydrogen-storing device 80 to Fig. 5 is described in detail.The hydrogen-storing device of this Fig. 5 constitutes the liquid hydrogen storing unit of storing behind the liquefaction of hydrogen in order to store more jumbo hydrogen.
As shown in Figure 5, hydrogen-storing device 80 possesses: the hold-up vessel 101 that is made of pressure vessels such as for example spherical storage tanks; Be connected and be connected the liquefying plant 102 of the inlet side of hold-up vessel 101 with pipe arrangement 91 from above-mentioned hydrogen tripping device 26; Be connected the gasification installation 103 of the outlet side of hold-up vessel 101; Be connected with gasification installation 103 and be connected to hydrogen compressor 104 on desulphurization reactor 10 and the hydrogenator 50,52,54 via above-mentioned pipe arrangement 92,93; Be used to control the controller 105 of the each several part of hydrogen-storing device 80.Wherein, liquefying plant 102 can make liquefaction of hydrogen by for example joule-thomson circulation isentropic expansion circulation or helium Brayton cycle thermodynamic cycle such as (helium Brayton cycle).In addition, gasification installation 103 possesses heat exchanger etc., can heat and gasify the liquefying hydrogen supplied with from hold-up vessel 101 and become hydrogen.Have, controller 105 is examples of controlling organization of the action (for example, the supply work of the storage work of hydrogen or hydrogen that supply with to store to the reaction unit that utilizes hydrogen etc.) of control hydrogen-storing device 80 again.
Action to the hydrogen-storing device 80 of Fig. 5 of formation like this describes below.When the normal operation of aforesaid liquid fuel synthesis system 1, same with the example of above-mentioned Fig. 4, store indicator signal to controller 105 inputs of hydrogen-storing device 80.So controller 105 carries out following control in order to store hydrogen in hold-up vessel 101: make liquefying plant 102 work, open the valve 106 of the inlet side of hold-up vessel 101, close the valve 107 of outlet side simultaneously.Thus, the part of the hydrogen that will discharge from hydrogen tripping device 26 supplies to liquefying plant 102 by pipe arrangement 91, and liquefying plant 102 makes the liquefaction of hydrogen of supply, and the storage pressure (for example 0.5MPaG) of this liquefying hydrogen with regulation is stored in the hold-up vessel 101.Then, in the moment of the liquefying hydrogen of having stored q.s, controller 105 stops the action of liquefying plant 102, closes the valve 106 of the inlet side of hold-up vessel 101, finishes storage work.
On the other hand, when the starting of aforesaid liquid fuel synthesis system 1, similarly supply with indicator signal to controller 105 inputs of hydrogen-storing device 80 with the example of Fig. 4.So, controller 105 gasifies and supplies with in order to be stored in liquefying hydrogen in the hold-up vessel 101 as described above, carry out following control: make 104 work of gasification installation 103 and hydrogen compressor,, open the valve 107 of outlet side with the state of the valve 106 of the inlet side of closing hold-up vessel 101.Thus, be stored in the liquefying hydrogen in the hold-up vessel 101, gasified by gasification installation 103, become hydrogen, and, by hydrogen compressor 83, this hydrogen is boosted to the specified pressure (for example 3.6MPaG) that is fit to bubble tower reactor 30, the hydrogen with this after boosted supplies to desulphurization reactor 10 and hydrogenator 50,52,54 by pipe arrangement 92,93.Like this, in the example of Fig. 5, by liquefaction of hydrogen is stored, can in hold-up vessel 101, store a large amount of hydrogen, in addition, during the starting of liquid fuel within synthesis system 1, the hydrogen that can at once the liquefying hydrogen gasification that is stored in the hold-up vessel 101 be formed supplies to required place in large quantities.
More than, the liquid fuel synthesis system 1 of present embodiment and the starting method of this liquid fuel synthesis system 1 are described in detail.According to present embodiment, by hydrogen-storing device 80 is set, during the normal operation of liquid fuel within synthesis system 1, the part of the hydrogen in the synthetic gas that will generate in reformer 12 is stored in the hydrogen-storing device 80, can guarantee that hydrogen is more than specified amount, when needs hydrogen, can be from hydrogen-storing device 80 instantaneous hydrogen supplies.Thereby, during the restarting of liquid fuel within synthesis system 1 etc., can utilize the reaction unit of hydrogen to supply with the hydrogen that is stored in the hydrogen-storing device 80 to hydrogenator 50,52,54 or desulphurization reactor 10 etc. immediately, therefore the required time before starting these reaction units that utilize hydrogen and normal operation can be foreshortened to minimum.Therefore, the starting time of liquid fuel synthesis system 1 integral body can be shortened significantly, thereby the production efficiency of liquid fuel goods such as petroleum naphtha, lam-oil, light oil can be improved.
More than, preferred embodiment being illustrated of the present invention with reference to accompanying drawing, the present invention is not limited to above-mentioned example certainly.Obviously, so long as those skilled in the art just can expect various modifications or revise example that these can certainly be interpreted as and belong to technical scope of the present invention in the scope of claim record.
For example, in the above-described embodiment, adopted Sweet natural gas, but also be not limited to this example, for example also can adopt other hydrocarbon materials such as pitch, residual oil as the hydrocarbon material that supplies to liquid fuel synthesis system 1.
In addition, in the above-described embodiment,, come the synthetic fluid hydrocarbon polymer by the FT building-up reactions, but the present invention is not limited thereto example as the building-up reactions in the bubble tower reactor 30.As the building-up reactions in the bubble tower reactor, for example, also can be applied to oxo process (carbonylation reaction) " RCH=CH
2+ CO+H
2→ RCH
2CH
2CHO ", the synthetic " CO+2H of methyl alcohol
2→ CH
3OH ", the synthetic " 3CO+3H of dme (DME)
2→ CH
3OCH
3+ CO
2" etc.
In addition, in the above-described embodiment, as the reaction unit that utilizes hydrogen, listed the example of desulphurization reactor 10, wax slop hydrocracking reactor 50, lam-oil and light oil distillate hydrofining reactor 52, naphtha fraction hydrofining reactor 54, but also be not limited to above-mentioned example, so long as the device that utilizes hydrogen to carry out the regulation reaction in the liquid fuel within synthesis system also can be above-mentioned device arbitrarily in addition.Specifically be, utilize the reaction unit of hydrogen also can be fuel cell for example, carry out the hydrogenation reaction (naphthalene → naphthalane) of naphthalene device, carry out aromatic hydrocarbons (benzene) hydrogenation reaction (benzene → hexanaphthene etc.) device or unsaturated fatty acids is carried out device of hydrogenation reaction etc.
In addition, in the above-described embodiment, as the reactor that synthetic gas is synthesized liquid hydrocarbon, adopted the tower suspension bed formula of bubble reactor, but the present invention also is not limited to this example, for example, also can adopt fixed bed type reactor etc. to carry out the FT building-up reactions.
The present invention relates to the starting method of liquid fuel synthesis system, wherein, this liquid fuel synthesis system possesses hydrocarbon material is reformed and generated with CO (carbon monoxide converter) gas and hydrogen and be the reformer of the synthetic gas of principal constituent, come the reactor of synthetic fluid hydrocarbon polymer and utilized the reaction unit that utilizes hydrogen that contained hydrogen carries out the regulation reaction in the synthetic gas generate in described reformer by CO (carbon monoxide converter) gas contained in the described synthetic gas and hydrogen; When the normal operation of described liquid fuel synthesis system, the part of hydrogen contained in the synthetic gas that generates in described reformer is separated and stored, when the starting of described liquid fuel synthesis system, the hydrogen that is stored in the described hydrogen-storing device is supplied to the described reaction unit that utilizes hydrogen.
According to the starting method of liquid fuel synthesis system of the present invention, can make and utilize the reaction unit of hydrogen to start rapidly, thereby can enhance productivity.
Claims (8)
1, a kind of starting method of liquid fuel synthesis system, wherein, this liquid fuel synthesis system possesses hydrocarbon material is reformed and generated with CO (carbon monoxide converter) gas and hydrogen and be the reformer of the synthetic gas of principal constituent, come the reactor of synthetic fluid hydrocarbon polymer and utilized the reaction unit that utilizes hydrogen that contained hydrogen carries out the regulation reaction in the synthetic gas generate in described reformer by CO (carbon monoxide converter) gas contained in the described synthetic gas and hydrogen; When the normal operation of described liquid fuel synthesis system, the part of hydrogen contained in the synthetic gas that generates in described reformer is separated and stored, when the starting of described liquid fuel synthesis system, the hydrogen that is stored in the described hydrogen-storing device is supplied to the described reaction unit that utilizes hydrogen.
2, the starting method of liquid fuel synthesis system according to claim 1, wherein, the described reaction unit that utilizes hydrogen comprises synthetic liquid hydrocarbon in described reactor is carried out the hydrogenator of hydrogenation and the hydrocarbon material that supplies to described reformer carried out any at least in the desulphurization reactor of hydro-desulfurization.
3, the starting method of liquid fuel synthesis system according to claim 1, wherein, described hydrogen separates by any at least method in pressure variation absorption method, hydrogen storage alloy absorption method and the membrane separation process.
4, the starting method of liquid fuel synthesis system according to claim 1, wherein, described reactor is the tower suspension bed formula of a bubble reactor.
5, a kind of liquid fuel synthesis system possesses:
Reformer, it is reformed to hydrocarbon material, and generating with CO (carbon monoxide converter) gas and hydrogen is the synthetic gas of principal constituent;
Reactor, it comes the synthetic fluid hydrocarbon polymer by CO (carbon monoxide converter) gas contained in the described synthetic gas and hydrogen;
Utilize the reaction unit of hydrogen, it utilizes, and contained hydrogen carries out the regulation reaction in the synthetic gas that generates in described reformer;
The hydrogen tripping device, its part to hydrogen contained in the synthetic gas that generates in described reformer is separated;
Hydrogen-storing device, it is stored by described hydrogen tripping device and separates the hydrogen that obtains;
Controlling organization, it supplies to the described reaction unit that utilizes hydrogen with the hydrogen that is stored in the described hydrogen-storing device when the starting of described liquid fuel synthesis system.
6, liquid fuel synthesis system according to claim 5, wherein, the described reaction unit that utilizes hydrogen comprises synthetic liquid hydrocarbon in described reactor is carried out the hydrogenator of hydrogenation and the hydrocarbon material that supplies to described reformer carried out any at least in the desulphurization reactor of hydro-desulfurization.
7, liquid fuel synthesis system according to claim 5, wherein, described hydrogen tripping device is by any at least method separating hydrogen gas in pressure variation absorption method, hydrogen storage alloy absorption method and the membrane separation process.
8, liquid fuel synthesis system according to claim 5, wherein, described reactor is the tower suspension bed formula of a bubble reactor.
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|---|---|---|---|
| JP2006096015 | 2006-03-30 | ||
| JP096015/2006 | 2006-03-30 | ||
| PCT/JP2007/056922 WO2007114276A1 (en) | 2006-03-30 | 2007-03-29 | Method for start-up of liquid fuel synthesis system, and liquid fuel synthesis system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101432393A true CN101432393A (en) | 2009-05-13 |
| CN101432393B CN101432393B (en) | 2013-03-27 |
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Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPWO2007114276A1 (en) |
| CN (1) | CN101432393B (en) |
| AU (1) | AU2007232925C1 (en) |
| MY (1) | MY149999A (en) |
| RU (1) | RU2430954C2 (en) |
| WO (1) | WO2007114276A1 (en) |
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| CN106460208A (en) * | 2014-05-26 | 2017-02-22 | 太阳火有限公司 | Hydrocarbon-production-apparatus and method for producing hydrocarbons with renewable electric energy |
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| JP5296478B2 (en) * | 2008-09-30 | 2013-09-25 | Ｊｘ日鉱日石エネルギー株式会社 | Rectification tower startup method |
| WO2010038392A1 (en) * | 2008-09-30 | 2010-04-08 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Bubble tower reactor and method of controlling bubble tower reactor |
| EA024240B1 (en) | 2010-03-25 | 2016-08-31 | Джэпэн Ойл, Гэз Энд Металз Нэшнл Корпорейшн | Start-up method for fractionator |
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| US6043288A (en) * | 1998-02-13 | 2000-03-28 | Exxon Research And Engineering Co. | Gas conversion using synthesis gas produced hydrogen for catalyst rejuvenation and hydrocarbon conversion |
| JP2002020102A (en) * | 2000-06-30 | 2002-01-23 | Mitsubishi Kakoki Kaisha Ltd | Method for starting and method for stopping hydrogen producing device |
| US6508931B1 (en) * | 2000-10-31 | 2003-01-21 | Chinese Petroleum Corporation | Process for the production of white oil |
| JP3647028B2 (en) * | 2001-02-19 | 2005-05-11 | 日本エア・リキード株式会社 | Liquid hydrogen production method and liquid hydrogen production equipment |
| US20030021743A1 (en) * | 2001-06-15 | 2003-01-30 | Wikstrom Jon P. | Fuel cell refueling station and system |
| US6946493B2 (en) * | 2003-03-15 | 2005-09-20 | Conocophillips Company | Managing hydrogen in a gas to liquid plant |
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2007
- 2007-03-29 MY MYPI20083787A patent/MY149999A/en unknown
- 2007-03-29 RU RU2008141284/04A patent/RU2430954C2/en not_active IP Right Cessation
- 2007-03-29 AU AU2007232925A patent/AU2007232925C1/en not_active Ceased
- 2007-03-29 JP JP2008508621A patent/JPWO2007114276A1/en active Pending
- 2007-03-29 WO PCT/JP2007/056922 patent/WO2007114276A1/en active Application Filing
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106460208A (en) * | 2014-05-26 | 2017-02-22 | 太阳火有限公司 | Hydrocarbon-production-apparatus and method for producing hydrocarbons with renewable electric energy |
| CN106460208B (en) * | 2014-05-26 | 2020-05-19 | 太阳火有限公司 | Hydrocarbon production plant and method for producing hydrocarbons using renewable electrical energy |
Also Published As
| Publication number | Publication date |
|---|---|
| MY149999A (en) | 2013-11-15 |
| AU2007232925C1 (en) | 2011-08-11 |
| WO2007114276A1 (en) | 2007-10-11 |
| JPWO2007114276A1 (en) | 2009-08-13 |
| CN101432393B (en) | 2013-03-27 |
| AU2007232925B2 (en) | 2010-12-09 |
| ZA200808244B (en) | 2010-01-27 |
| AU2007232925A1 (en) | 2007-10-11 |
| RU2430954C2 (en) | 2011-10-10 |
| RU2008141284A (en) | 2010-04-27 |
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