CN1611565A - Liquid fuel producing technique from synthetic gas - Google Patents
Liquid fuel producing technique from synthetic gas Download PDFInfo
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- CN1611565A CN1611565A CN 200310108146 CN200310108146A CN1611565A CN 1611565 A CN1611565 A CN 1611565A CN 200310108146 CN200310108146 CN 200310108146 CN 200310108146 A CN200310108146 A CN 200310108146A CN 1611565 A CN1611565 A CN 1611565A
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 39
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 150
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- 230000000171 quenching effect Effects 0.000 claims description 45
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- 238000003672 processing method Methods 0.000 claims description 18
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- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
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- 238000004517 catalytic hydrocracking Methods 0.000 claims description 8
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- 239000003245 coal Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a kind of technology for manufacturing liquid fuel with synthetic gas, which contains three parts that are Fisher-Tropsch synthetic unit, C3-C5 reclaiming unit and oil refining unit. The Fisher-Tropsch synthetic unit is divided in two levels, whose products are all paraffin and condensate; The virgin gas of senior Fisher-Tropsch synthesis is the tail gas of primary Fisher-Tropsch synthesis; Part tail gas of the two synthetic units circulates; The tail gas of senior Fisher-Tropsch synthesis run into C3-C5 reclaiming unit; The C3-C5 reclaiming unit can reclaim most of the constituents with more than C3 in the tail gas by deep refrigeration; The constituents get into the oil refining unit with paraffin and condensate produced in two levels Fisher-Tropsch synthetic unit in order to proceed liquid fuel production. Compared with existing technology, the invention has the advantages such as various categories of products, high procedure carbon efficiency, low cost, and so on.
Description
Technical field
The present invention relates to the production method of liquid fuel, relate in particular to a kind of processing method of producing liquid fuel with synthetic gas.
Background technology
In recent years, along with the exploitation of countries in the world to petroleum resources, petroleum resources are fewer and feweri, and are particularly all the more so for a lot of petroleum resources original just deficient country such as China.A lot of national oil rely on import in a large number, and the not only heavy economical load of back, and jeopardize self energy security of country is subjected to paying close attention to widely so carbon back raw material beyond the exploitation oil such as coal, Sweet natural gas, coal-seam gas etc. are produced the novel process of liquid fuel.The reaction that generates higher hydrocarbon with synthetic gas under catalyst action becomes expense-holder building-up reactions, and the source of synthetic gas is very extensive, both can derive from coal, also can derive from Sweet natural gas, oil-poor or the country that rich gas is oil-poor for those rich coals, products such as diesel oil, gasoline are produced in support expense-holder building-up reactions exploitation with synthetic gas novel process has very important significance.
The seventies in last century, U.S. Mobil company has succeeded in developing the ZSM-5 molecular sieve catalyst, and relies on this catalyzer that former Fischer-Tropsch process is improved, after successfully developed two sections Fischer-Tropsch process of slurry attitude bed.First section of this two sections building-up process are with behind the synthetic gas synthesizing methanol, again at second section by ZSM-5 catalyzer synthetic gasoline.U.S. Mobil company and to adopt this technology to build with the Sweet natural gas in New Zealand in 1985 be the full scale plant of raw material production gasoline.But the transformation efficiency of above-mentioned technology two-stage reaction is all lower, gasoline production cost height.
Mitsubishi heavy industry and COSMO oil company developed jointly with the technology of synthetic gas through the dme synthetic gasoline at the beginning of the eighties in last century.First section of this technology adopts high pressure fixed bed dimethyl ether synthesis and other oxygenatedchemicalss, and two sections used the low pressure fluidized-bed that dimethyl ether conversion is gasoline, but this method is not implemented on the full scale plant.
Chinese patent CN1137058A discloses the method for Shanxi coalification institute of Chinese Academy of Sciences two-stage method synthetic gasoline.This technology is to be raw material with the coal based synthetic gas, and through two sections synthetic gasolines, tail gas adopts the two-section joint single loop, and first section is adopted the ultra-fine ionic catalyst synthesizing low-carbon of F-Mn alkene, and second section is adopted ZMS-5 molecular sieve catalyst synthetic gasoline.Yield of gasoline can reach 142g/Nm
3(CO+H
2).
More than various handicraft products mainly based on gasoline, product is comparatively single, production cost is higher, carbon efficiencies is low.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of product category of production many for the defective that overcomes above-mentioned prior art existence, process carbon efficiencies height, the processing method with synthetic gas production liquid fuel that cost is low.
Purpose of the present invention can be achieved through the following technical solutions: a kind of processing method of producing liquid fuel with synthetic gas, this processing method is to use the synthetic gas that contains a large amount of hydrogen and carbon monoxide, produce paraffin and condensation product by taking-hold in the palm building-up reactions, again paraffin and the condensation product of producing finally obtained diesel oil, gasoline, kerosene, petroleum naphtha and liquefied petroleum gas product through hydrocracking, the fractionated deep-processing process of reforming, it is characterized in that the concrete processing step of this processing method is as follows:
A) synthetic gas from gasification or conversion of natural gas takes-holds in the palm building-up reactions by two-stage, some loops back this stage reactor or preceding stage reactor mixes with virgin gas behind the tail gas separated product of every order reaction, and second stage expense-holder synthesis tail gas enters C3-C5 and reclaims the unit;
B) paraffin of expense-holder building-up reactions generation shifts out reactor at the liquid-solid separator by inside reactor;
C) granules of catalyst and the separating high-temp condensation product of wherein carrying secretly by a quenching column flush away from the reactor head expellant gas;
D) go out quenching column gas after overcooling, isolate cryogenic condensation thing, reaction water and tail gas by triphase separator;
E) C3-C5 reclaims in the unit, adopts degree of depth method of cooling that the heavy constituent that take-hold in the palm in the synthesis tail gas are separated, and forms final tail gas;
F) take-hold in the palm paraffin, condensation product and C3-C5 stream thigh that synthesis unit is produced, through hydrocracking, produce qualified diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas product after isomerization and the fractionation in refinery unit.
Described expense-holder synthesis unit is divided into two-stage, and product is paraffin, high temperature condensation product, cryogenic condensation thing and reaction water.
Described two-stage expense-holder building-up reactions tail gas recycle ratio can be adjusted, and the recycle ratio scope is 0-3, and the recycled offgas of two-stage reactor can adopt different recycle ratios.
The recycled offgas of described two-stage expense-holder building-up reactions adopts gas compressor to compress conveying, to increase its pressure.
The source of described synthetic gas both can come from coal generating gas, also can come from conversion of natural gas.
Described expense-holder synthesis reactor is a paste state bed reactor, and this inside reactor is equipped with liquid-solid separation device directly isolates paraffin in reactor.
Described expense-holder building-up reactions adopts drum to produce steam and removes reaction heat, and temperature of reactor is controlled by regulating drum pressure.
A described quenching column bottom liquid product part loops back quenching column, all the other are as high temperature condensation product product, recycle stock is used for unstripped gas is carried out the secondary preheating simultaneously, and Quench and is washed to remove wherein contained solid particulate this gas from the gas of reactor head after the heat exchange.
Also comprise and adopt quenching column top gas product to come unstripped gas is carried out the one-level preheating.
Described firsts and seconds expense-holder synthesis pressure is 20-50bar, and temperature of reaction is 200-300 ℃.
Compared with prior art, the present invention is that the synthetic gas that produces with coal generating gas or syngas production from NG is a raw material, takes-hold in the palm synthesis reactor and subsequent products tripping device by two-stage, produces paraffin, condensation product.Two sections tail gas circulate by different recycle ratios.Paraffin and condensation product are produced fuel products such as the diesel oil that needs, gasoline, kerosene by oil refining process.Residual exhaust burning back produces steam and is used for generating.The present invention has adopted the two-stage reaction process, and the product of every order reaction process all is a higher hydrocarbon, every grade of tail gas circulation, and two-stage reactor is paste state bed reactor, adopts the low temperature iron-based to take-Tropsch synthesis catalyst.CO transformation efficiency of the present invention can reach more than 97%, CO+H
2Total conversion rate can reach 95%, and the oil product yield reaches 180g/Nm
3(CO+H
2), system's carbon efficiencies and thermo-efficiency are all than other technology height.In addition, it is applied widely that the present invention has unstripped gas, and the product category of production is many, process carbon efficiencies height, characteristics such as cost is low.
Description of drawings
Fig. 1 is of the present invention expense-hold in the palm process flow sheet of synthesis unit;
Fig. 2 reclaims unitary process flow sheet for C3-C5 of the present invention;
Fig. 3 is the process flow sheet of refinery unit of the present invention;
Fig. 4 is the process flow sheet of the embodiment of the invention 2 expenses-holder synthesis unit;
Fig. 5 is the process flow sheet of the embodiment of the invention 3 expenses-holder synthesis unit.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments.
Fig. 1, Fig. 2, Fig. 3 expense of being respectively-holder synthesis unit, C3-C5 reclaim the schema of unit, refinery unit.In Fig. 1,,, form the virgin gas 1 of definite composition through desulfurization, deoxidation, conversion and carbon rejection process from the synthetic gas of coal generating gas or Sweet natural gas.Virgin gas pressure is about 20-50bar, and virgin gas is mixed into gas 2 with one-level recycled offgas 18, and gas 2 carries out preheating by two sections interchanger, and the heat of these two sections interchanger preheatings comes from the top gas 6 of quenching column B and the cold shot liquid 7 of bottom cycle respectively.Through after these two sections preheatings, unstripped gas is preheating to more than 120 ℃, enters into expense-holder synthesis reactor A.Every grade of expense-holder synthesis reactor is composed in parallel by one or more reactors, establishes liquid-solid separator in the reactor.Because expense-holder building-up reactions is a strong exothermal reaction, reaction heat adds feedwater by the coil pipe in the reactor, produces steam by drum reaction heat is removed, and temperature of reactor is regulated by the pressure-controlling of drum.The one-level paraffin 4 that expense-holder building-up reactions generates directly shifts out reactor by the liquid-solid separator in the reactor, enters into the paraffin receiving tank, and cooling back one-level paraffin wax product is as the raw material of oil product deep processing.The gas 5 of reactor head outlet enters into one-level quenching column B.The quenching column product is divided into high temperature condensation product and overhead gas at the bottom of the tower, a bottom product part by quenching column recycle pump E and two sections interchanger coolings after, return in the quenching column as Quench liquid 10, another part is as one-level high temperature condensation product product 8.One-level quenching column condensation product internal circulating load is by quenching column tower top temperature and the decision of whole quenching column thermal equilibrium.Cooled cyclic high-temperature condensation product is when carrying out cold shock to reactor outlet gas, and the granules of catalyst of being carried secretly is removed in washing.Quenching column overhead gas 6 is reduced to about 40 ℃-60 ℃ through three sections interchanger cooling back temperature, enters into one-level high-pressure separator C.Liquid separates in high-pressure separator with gas, and the oil reservoir in the liquid phase is as one-level cryogenic condensation produce product 15, and water layer arrives water treatment system as first order reaction water 14.Separator top expellant gas 16, a part are mixed into A reactor A through after the compressor compresses with virgin gas as circulation gas 17, and rest part is mixed into second reactor F as the virgin gas 19 of second order reaction with second order reaction circulation gas 36.
It is similar with one-level that secondary takes-hold in the palm the synthesis technique flow process, and virgin gas 19 is mixed the back and is preheating to more than 120 ℃ by the pre-hot gas of two section feedings with secondary recycled offgas 36, and preheating quantity is from circulating liquid 25 and the top gas 24 of secondary quenching column G.Carry out expense-holder building-up reactions after entering reactor F, secondary paraffin 22 separates by the liquid-solid separator of inside reactor, enters the paraffin receiving tank, and the cooling back is as the secondary paraffin wax product.Reactor head works off one's feeling vent one's spleen 23, enters into secondary quenching column G.A secondary quenching column bottoms part is by quenching column recycle pump J and two-stage interchanger postcooling, and it is interior as Quench liquid 28 to return quenching column, and another part is as secondary high temperature condensation product product 26.Secondary quenching column condensation product internal circulating load is by quenching column tower top temperature and whole secondary quenching column thermal equilibrium control.Secondary quenching column overhead gas 24 is reduced to 40 ℃-60 ℃ through three sections interchanger cooling back temperature, enter into secondary high-pressure separator H, in this separator H, gas-liquid two-phase is separated, oil reservoir in the liquid phase is as secondary cryogenic condensation thing 33, water layer is to enter into water treatment system after second order reaction water 32 and first order reaction water 14 merge.Secondary high-pressure separator top gas 34, a part be as circulation gas 35, through the compression of secondary recycle compressor, and returns second reactor after secondary virgin gas is mixed, and a remaining part enters into C3-C5 recovery unit as second order reaction tail gas 37.
In Fig. 2, secondary takes-holds in the palm synthesis tail gas 38 through overcooling, dehydration is cooled to about-30～-50 ℃, and above component of C3 and partial oxide are cooled and get off to become liquid in the tail gas, form gas-liquid mixed logistics 43, by gas-liquid separator J, liquid portion 46 enters gas stripping column K, with the most carbonic acid gas 47 in nitrogen or the steam gas proposition liquid, all the other form logistics 51 and enter refinery unit as condensation product 49 after pump pressurization and heat exchange.Gas-liquid separator J top gas becomes final tail gas 45, and this tail gas carries out transformation absorption, separates hydrogen wherein, is used for the raw hydrogen of expense-holder sintetics deep processing.Isolate tail gas the acting as a fuel of hydrogen with technological process.
In Fig. 3, the material 52 by synthetic paraffin 53, high temperature condensation product and cryogenic condensation thing that produces of two-stage expense-holder and C3-C5 component are merged together mixes with hydrogen, and the hydrogen source is fresh hydrogen 57 and circulating hydrogen 66.Mixed material is by hydrogenator M and hydrocracking reactor N, through reactions such as hydrocracking, isomerization, reformations, and water washing with separate a series of heat transfer process such as flash distillation, divide two bursts of material heavy constituent 78, light constituent 75 enters into separation column T and petroleum naphtha stabilizer tower U respectively, separation column T output oil product is a diesel component, and separation column T is separated portion 85 not, by mixing with fresh paraffin 53 and condensation product 52 behind the recycle pump.Fractionation Tata top light constituent 89 also proceeds to petroleum naphtha stabilizer tower U to be separated, and isolates the burning that acts as a fuel of light constituent 83 and 91 that 93, two towers of petroleum naphtha 95 and liquefied petroleum gas (LPG) speed to emit.
Embodiment 1
This embodiment has adopted as Fig. 1, Fig. 2, the flow process of Fig. 3.Virgin gas is the synthetic gas that texaco coal-water slurry gasification produces, and is 40 ℃ through temperature behind the low-temperature rectisol, and pressure is 31bar, and gas composition is H
2: 60%, CO:39%, CO
2: 0.18%, Ar:0.15%, CH
4: 0.03%, N
2: 0.63%, tolerance is 0.393E6Nm
3/ h, one-level recycled offgas 17 pressure after overdraft also is 31bar, mixing the back temperature with one-level virgin gas 1 is 44 ℃, pressure is 31bar, through one section heat exchange of A reactor feeding gas, the unstripped gas temperature rises to 108 ℃, then by the heat exchange of A reactor charging secondary, unstripped gas is preheating to 140 ℃, enter into one-level synthesis reactor A, one-level synthesis reactor A is two reactor parallel connections, each reactor all is a paste state bed reactor, the reactor height is 27m, internal diameter 3.90m, low temperature ferrum-based catalyst loading amount is 48.54 tons, working pressure is 30bar, service temperature is 235 ℃, two reactors of one-level are isolated 29.98 tons/hour in paraffin by liquid-solid separator in the reactor, gas 5 from reactor head enters into one-level quenching column B, and quenching column circulation Quench liquid 10 temperature are 113 ℃, and overhead gas 6 temperature are 156.5 ℃, column bottom temperature is 212 ℃, the high temperature condensation product product 8 of quenching column bottom product part conduct, output is 3.39 tons/hour, another part enters Quench cat head with recycle pump as Quench liquid 7 after overcooling.One section preheating is cooled to 143.1 ℃ earlier to the quenching column top gas through A reactor, be cooled to 60 ℃ by one-level quenching column de-salted water well heater again, after being cooled to 40 ℃ by one-level quenching column water cooler at last, enter high-pressure separator C, in high-pressure separator, mixture is separated into gas-liquid two-phase, and the oil reservoir in the liquid phase is a cryogenic condensation thing 15, output is 11.17 tons/hour, and water 14 output are 51.60 tons/hour in the liquid phase.Separator top tail gas pressure is reduced to about 25.5bar, a part of as returning one-level synthesis reactor A after the recycled offgas 17 process compressor compresses with after one-level virgin gas 1 is mixed, internal circulating load is 0.2 with the ratio of virgin gas, and a remaining part enters second stage expense-holder building-up reactions as the virgin gas 19 of second order reaction.
The synthesis technique and first segment base are taken-held in the palm in the second stage, and this is similar.Virgin gas 19 successively is heated to 86 ℃ and 140 ℃ through two sections preheater preheatings after mixing with recycled offgas 36, enter into secondary expense-holder synthesis reactor F, second reactor is formed in parallel by two paste state bed reactors equally, each reactor height is 27m, internal diameter is 3.60m, 36.59 tons of interior dress low temperature ferrum-based catalysts.Reactor operating pressure is 25bar, and service temperature still is 235 ℃, and the paraffin total amount of output is 11.84 tons/hour in two reactors.Reactor head gas 23 enters secondary quenching column G, quenching column top tray temperature is 130 ℃, quenching column circulation Quench liquid 28 temperature are 113 ℃, the bottom liquid temperature is 189 ℃, a bottoms part is cooled to 113 ℃ as two sections preheaters of Quench liquid second reactor and secondary quenching column cycle heat exchange device cooling back as Quench liquid, send into the Quench cat head with pump J, another part is as secondary high temperature condensation product product 26, and output is 2.70 tons/hour.At first one section preheating is cooled to 121 ℃ to quenching column top output gas 24 through second reactor, after successively being cooled to 80 ℃ and 40 ℃ then by secondary quenching column de-salted water well heater and secondary quenching column water cooler, enter secondary high-pressure separator H, the secondary high-pressure separator is isolated liquid and gas, oil reservoir 33 in the liquid phase is secondary cryogenic condensation produce product, output is 7.25 tons/hour, and water layer 32 is a reaction water, and output is 27.29 tons/hour.The gaseous tension that come out from the secondary high-pressure separator this moment is reduced to about 20.0bar, wherein a part of the mixing with secondary virgin gas 19 to 25.5bar through compressor compresses of gas returned second reactor F, recycle ratio is 1, and rest part enters C3-C5 and reclaims the unit recovery above component of C3 wherein.
The tail gas that enters in the C3-C5 recovery unit is cooled to-35 ℃, through a gas-liquid separator J, top gas is through forming final tail gas after the heat exchange, tail gas is through transformation absorption, separated hydrogen can be used as the feed hydrogen of hydrocracking, produces steam after the remaining gaseous combustion and drives the turbo-generator generating.Bottom liquid is carried through nitrogen gas again, the C3 above component of gas stripping column K bottom product 49 for reclaiming, and total amount is about 5.28 tons/hour, and cat head is most of CO
2This part material is same, secondary paraffin, and I and II high temperature cryogenic condensation thing enters into refinery unit together and carries out oil product processing.
In refinery unit processing, raw material is through after hydrogenation reaction, hydrocracking and the isomerization reaction, after water washing, enter separation column and naphtha splitter, isolate fuel such as diesel oil, petroleum naphtha and liquefied petroleum gas (LPG), the light constituent of process loss, the gas that acts as a fuel equally is used for generating.Whole process is produced 48.17 tons/hour of diesel oil altogether, 16.23 tons/hour of petroleum naphthas, 4.79 tons/hour of liquefied petroleum gas (LPG).
Embodiment 2
It is different with embodiment 1 that embodiment 2 takes-hold in the palm composite part, and C3-C5 recovery unit is identical with embodiment 1 with refinery unit, sees Fig. 4 for expense-holder synthesis unit of embodiment 2.Inlet virgin gas 96 compositions, temperature and pressure are all identical with embodiment, main difference is among the embodiment 2, one-level expense-holder synthesis tail gas does not circulate and all synthesizes virgin gas 111 as secondary expense-holder, and one-level expense-holder synthesis reactor feeding gas 115 is made of after compression virgin gas 111 and secondary tail gas part circulation gas 130.A reactor V operation condition is pressure 30bar, 235 ℃ of temperature, and the high 27m of reactor, diameter are 3.90m, 44.42 tons of catalyzer loading amounts.From 27.75 tons/hour of first step reactor separating paraffins, 3.14 tons/hour of quenching column W separating high-temp condensation products, high-pressure separator X separates 10.54 tons/hour of cryogenic condensation things, 48.59 tons/hour of reaction water.One-level tail gas 111 takes-holds in the palm synthetic virgin gas as secondary and mixes with the secondary recycled offgas, and recycle ratio is 1, and the secondary Fischer-Tropsch process is consistent with the secondary Fischer-Tropsch process of embodiment 1.Secondary expense-holder synthesis reactor operational condition is pressure 26bar, 235 ℃ of temperature, and the high 27m of reactor, diameter are 4.46m, 54.05 tons of catalyzer loading amounts.From 13.05 tons/hour of second stage reactor A A separating paraffins, 3.15 tons/hour of quenching column AB separating high-temp condensation products, high-pressure separator AC separates 8.09 tons/hour of cryogenic condensation things, 30.12 tons/hour of reaction water.A secondary tail gas part 130 loops back second reactor, and a part 112 loops back the A reactor recycle ratio and is respectively 1 and 0.2.It is identical that follow-up C3-C5 reclaims unit and refinery unit and embodiment 1,47.89 tons/hour of final production diesel oil, 16.10 tons/hour of petroleum naphthas, 4.55 tons/hour of liquefied petroleum gas (LPG).
Embodiment 3
Embodiment 3 takes-hold in the palm composite part and embodiment 1,2 is different, and it is also identical with embodiment 1 with refinery unit that C3-C5 reclaims the unit, sees Fig. 5 for expense-holder synthesis unit of embodiment 3.Inlet virgin gas 133 compositions, temperature and pressure are all identical with embodiment, main difference is among the embodiment 3,20% one-level virgin gas 170 goes directly that second stage Fischer-Tropsch is synthetic to be mixed with one-level expense-holder synthesis tail gas 148 and secondary recycled offgas 168, and logical embodiment 2 the same circulations of one-level tail gas are all synthesized virgin gas 148 as secondary expense-holder, and remaining one-level virgin gas is mixed with the tail gas 168 that secondary loops back as the synthetic feeding gas 152 of one-level expense-holder.A reactor AF operational condition is pressure 30bar, 235 ℃ of temperature, and the high 27m of reactor, diameter are 3.83m, 41.60 tons of catalyzer loading amounts.From 26.45 tons/hour of first step reactor A F separating paraffins, 2.86 tons/hour of quenching column AG separating high-temp condensation products, high-pressure separator AH separates 9.11 tons/hour of cryogenic condensation things, 46.37 tons/hour of reaction water.One-level tail gas 148 takes-holds in the palm synthetic virgin gas as secondary and mixes with secondary recycled offgas 168 and part one-level virgin gas, and secondary tail gas recycle ratio is 1, and the secondary Fischer-Tropsch process is consistent with the secondary Fischer-Tropsch process of embodiment 1.Secondary expense-holder synthesis reactor operational condition is pressure 26bar, 235 ℃ of temperature, and the high 27m of reactor, diameter are 3.87m, 34.79 tons of catalyzer loading amounts.From 14.01 tons/hour of second stage reactor A J separating paraffins, 4.05 tons/hour of quenching column AK separating high-temp condensation products, high-pressure separator AL separates 9.27 tons/hour of cryogenic condensation things, 33.31 tons/hour of reaction water.A secondary tail gas part 167 loops back second reactor AJ, and a part 149 loops back A reactor A, and recycle ratio is respectively 1 and 0.2.It is identical that follow-up C3-C5 reclaims unit and refinery unit and embodiment 1,47.62 tons/hour of final production diesel oil, 16.01 tons/hour of petroleum naphthas, 4.38 tons/hour of liquefied petroleum gas (LPG).
Foregoing has been described the preferred embodiments of the invention; but should be understood to also have many adjustable places; take-hold in the palm the synthesis tail gas recycle ratio as two-stage; every grade of Recycle design and every stage reactor number and sizes etc. of taking-holding in the palm synthesis tail gas, these are improved one's methods all should be in protection scope of the present invention.
Claims (10)
1. processing method of producing liquid fuel with synthetic gas, this processing method is to use the synthetic gas that contains a large amount of hydrogen and carbon monoxide, produce paraffin and condensation product by F-T synthesis reaction, again paraffin and the condensation product of producing finally obtained diesel oil, gasoline, kerosene, petroleum naphtha and liquefied petroleum gas product through hydrocracking, the fractionated deep-processing process of reforming, it is characterized in that the concrete processing step of this processing method is as follows:
A) synthetic gas from gasification or conversion of natural gas passes through the two-stage F-T synthesis reaction, some loops back this stage reactor or preceding stage reactor mixes with virgin gas behind the tail gas separated product of every order reaction, and second stage fischer-tropsch synthesis tail gas enters C3-C5 and reclaims the unit;
B) paraffin of F-T synthesis reaction generation shifts out reactor at the liquid-solid separator by inside reactor;
C) granules of catalyst and the separating high-temp condensation product of wherein carrying secretly by a quenching column flush away from the reactor head expellant gas;
D) go out quenching column gas after overcooling, isolate cryogenic condensation thing, reaction water and tail gas by triphase separator;
E) C3-C5 reclaims in the unit, adopts degree of depth method of cooling that the heavy constituent in the fischer-tropsch synthesis tail gas are separated, and forms final tail gas;
F) paraffin of fischer-tropsch synthesis unit production, condensation product and C3-C5 stream thigh through hydrocracking, are produced qualified diesel oil, gasoline, kerosene, petroleum naphtha, liquefied petroleum gas product in refinery unit after isomerization and the fractionation.
2. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 is characterized in that described fischer-tropsch synthesis unit is divided into two-stage, and product is paraffin, high temperature condensation product, cryogenic condensation thing and reaction water.
3. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 and 2, it is characterized in that, described two-stage F-T synthesis reaction tail gas recycle ratio can be adjusted, and the recycle ratio scope is 0-3, and the recycled offgas of two-stage reactor can adopt different recycle ratios.
4. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 and 2 is characterized in that the recycled offgas of described two-stage F-T synthesis reaction adopts gas compressor to compress conveying, to increase its pressure.
5. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 is characterized in that the source of described synthetic gas both can come from coal generating gas, also can come from conversion of natural gas.
6. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 and 2, it is characterized in that, described F-T synthesis reaction device is a paste state bed reactor, and this inside reactor is equipped with liquid-solid separation device directly isolates paraffin in reactor.
7. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 and 2 is characterized in that, described F-T synthesis reaction adopts drum to produce steam and removes reaction heat, and temperature of reactor is controlled by regulating drum pressure.
8. according to claim 1 or 3 described a kind of processing methodes of producing liquid fuel with synthetic gas, it is characterized in that, a described quenching column bottom liquid product part loops back quenching column, all the other are as high temperature condensation product product, recycle stock is used for unstripped gas is carried out the secondary preheating simultaneously, Quench is from the gas of reactor head after the heat exchange, and this gas is washed to remove wherein contained solid particulate.
9. according to claim 1 or 3 described a kind of processing methodes of producing liquid fuel, it is characterized in that, also comprise and adopt quenching column top gas product to come unstripped gas is carried out the one-level preheating with synthetic gas.
10. a kind of processing method of producing liquid fuel with synthetic gas according to claim 1 and 2 is characterized in that described firsts and seconds fischer-tropsch synthesis pressure is 20-50bar, and temperature of reaction is 200-300 ℃.
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