CN101863728A - Fischer-Tropsch synthesis method - Google Patents
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Abstract
The invention provides a Fischer-Tropsch synthesis method. The invention adopts two Fischer-Tropsch synthesis reaction vessels in serial connection, wherein the first Fischer-Tropsch synthesis reaction vessel is a slurry bed reaction vessel, and the second Fischer-Tropsch synthesis reaction vessel is a fixed bed reaction vessel. Outflow materials of the first Fischer-Tropsch synthesis reaction vessel fully or partially enter the second Fischer-Tropsch synthesis reaction vessel for carrying out synthesis reaction, and H2 and/or CO is injected between the two Fischer-Tropsch synthesis reaction vessels for regulating the molar ratio of H/C at an inlet of the second Fischer-Tropsch synthesis reaction vessel. The method provided by the invention overcomes the defects of great axial temperature difference, obvious heat point and difficult control of the reaction temperature of the fixed bed Fischer-Tropsch synthesis reaction vessel, and simultaneously ensures that the proportion of paraffin products in the products can not be reduced.
Description
Technical field
The present invention relates to a kind of is that raw material is by the synthetic method of producing liquid hydrocarbon of Fischer-Tropsch, specifically a kind of Fischer-Tropsch synthesis method of two reactors in series with the synthetic gas.
Background technology
Oil is the grand strategy goods and materials that ensure economic life line of the country and political security.Since the last century the nineties, China's oil consumption constantly increases, and substantially exceeds the rate of growth of the crude production same period, has to rely on the deficiency of providing domestic resource by import.Since China in 1993 became net import of oil state, the oil insufficiency of supply-demand enlarged year by year, and crude oil in China import in 2007 surpasses 1.6 hundred million tons, and externally interdependency surpasses 45%.So large-scale petroleum import has increased the degree of dependence of China to foreign oil, and the fluctuation of international petroleum market and variation will directly influence the safety of China's economy and even politics with stable.Therefore, China must walk the road of resource diversification strategically, greatly develops alternative petro-technology, reduces the China's oil risk.
Various to contain hydrocarbon resource be that raw material production goes out synthetic gas with Sweet natural gas, pitch, coal, biomass etc., with the synthetic gas be again raw material by the synthetic liquefied hydrocarbon of producing of Fischer-Tropsch, be one and well substitute petro-technology.Its product oil product mainly is made up of straight chain hydrocarbon, and after upgrading processing, the product naphtha fraction is a fine preparing ethylene by steam cracking raw material, and the triolefin yield is about 60 heavy %; Sulphur content of diesel fraction is less than 3 μ g/g, and nitrogen content is less than 0.5 μ g/g, and cetane value can satisfy the harshest existing diesel oil standard more than 74; Tail oil can be used as the raw material that generates III class or IV lubricant base, has high added value.Along with the raising of people's environmental consciousness, country will make stricter requirement to diesel oil, and the synthetic diesel product of producing of Fischer-Tropsch can be used as the blend component and the mediation of second-rate hydrofining diesel oil of high hexadecane value, low arene content and produces qualified diesel product.
Mainly adopt fixed-bed reactor and paste state bed reactor based on the Fischer-Tropsch synthesis process of producing intermediate oil and wax product, the two all has himself characteristic.Calandria type fixed bed Fischer-Tropsch synthetic operation is simple, and it is no problem fully that catalyzer separates with product; Liquid product separates from exit flow easily, and the production of suitable intermediate oil and wax especially is fit to produce wax product.Fixed bed Fischer-Tropsch synthetic weak point mainly is the heat-obtaining problem, owing to emit a large amount of heats in the reaction process, and the granular size of fixed bed catalyst has determined reaction process to have stronger diffusional effect, and heat is difficult for shifting out, and careless manipulation will cause the beds overtemperature.Because its heat-obtaining restriction, fixed-bed reactor can not design too big, have determined that the working ability of separate unit fixed-bed reactor is less.
But the slurry bed ft synthetic reactor sharpest edges are reactants mixes isothermal operation, thereby available higher average operation temperature and obtain higher speed of reaction adopts this reactor operation not to be prone to overheating problem, and single reactor productivity is bigger.But adopting the shortcoming of slurry bed ft synthetic reactor is catalyzer and product separation difficulty, and the quality of product wax is not as fixed bed wax product in addition.
CN1332744C discloses the reactor assembly of several reaction members in parallel.It comprises one or more shared reactant feed lines, two or more one reactor and one or more shared product outfall pipeline.Its reactor types adopts the multitube fixed bed.Adopt this method, promptly can improve the throughput of factory by the mode of a plurality of reactor parallel operations.
CN1948438A discloses a kind of two stage Fischer-Tropsch synthesis method.This method adopts the two reactor flow process, and two reactor is paste state bed reactor.The C1-C4 of the part tail gas of first section reactor enters second section reactor after being converted into synthetic gas through natural gas auto-thermal oxidation preparing synthetic gas method.The synthetic gas transformation efficiency of this inventive method is higher than 96%, and the productive rate of methane is lower than 3%.
US5827902 discloses a kind of multi-stage type Fischer-Tropsch synthesis method, and this method takes the placed in-line mode of a plurality of paste state bed reactors to operate, and number of reactors is more than at least 2.
US7432310B2 discloses a kind of method of synthin.This method adopts two conversion zones, and first conversion zone is a three-phase low-temp reaction section, in paste state bed reactor; Second conversion zone is a two-phase pyroreaction section, in fluidized-bed reactor.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of Fischer-Tropsch synthesis method, overcome that fixed bed Fischer-Tropsch synthesis device axial temperature difference is big, focus obviously reaches the uppity shortcoming of temperature of reaction, guarantee that simultaneously the ratio of paraffin wax product in the product can not reduce.
Method provided by the invention may further comprise the steps:
(1) synthetic gas enters the first Fischer-Tropsch synthesis device, carries out building-up reactions in the first Fischer-Tropsch synthesis device,
(2) all or part of first Fischer-Tropsch synthesis device effluent enters the second Fischer-Tropsch synthesis device and carries out building-up reactions,
(3) the second Fischer-Tropsch synthesis device effluent is separated, is separated into liquid hydrocarbon II, water II and gas II,
(4) step (3) gained gas II is partly discharged, remaining gas II loops back the first Fischer-Tropsch synthesis device and/or the second Fischer-Tropsch synthesis device,
(5) between the first Fischer-Tropsch synthesis device and the second Fischer-Tropsch synthesis device, inject H
2And/or CO, to regulate the second Fischer-Tropsch synthesis device ingress H/C mol ratio;
The described first Fischer-Tropsch synthesis device is a paste state bed reactor, and the described second Fischer-Tropsch synthesis device is fixed-bed reactor.
Wherein a kind of optimized technical scheme of the present invention is: the first Fischer-Tropsch synthesis device effluent all enters the second Fischer-Tropsch synthesis device and proceeds building-up reactions after removing catalyzer.
The another kind of optimized technical scheme of the present invention is: the first Fischer-Tropsch synthesis device effluent separates, and is separated into liquid hydrocarbon I, water I and gas I, and described gas I and optional partially liq hydro carbons I enter the second Fischer-Tropsch synthesis device and carry out building-up reactions.
Described gas I or gas II comprise CH
4, C
2H
4, C
2H
6, C
3H
6, C
3H
8, C
4H
8, C
4H
10, H
2, CO, CO
2In one or more.
Described liquid hydrocarbon I or liquid hydrocarbon II comprise C
5+Above hydro carbons.
Described liquid hydrocarbon I comprises cryogenic condensation thing and high temperature condensation product, and the final boiling point of described cryogenic condensation thing is not more than 450 ℃.The final boiling point of preferred described cryogenic condensation thing is not more than 200 ℃.
Described high temperature condensation product initial boiling point is not less than 150 ℃, and final boiling point is not less than 600 ℃.
In the another kind of optimized technical scheme of the present invention, among the described liquid hydrocarbon I that enters the second Fischer-Tropsch synthesis device, comprise all or part of described cryogenic condensation thing.
Synthetic gas of the present invention can be produced by coal, Sweet natural gas or organism, H in the synthetic gas
2With the volume ratio of CO be 1: 1～4: 1, be preferably 1.5: 1～2.5: 1.
The described first Fischer-Tropsch synthesis device is provided with the catalyzer filtering system, comprises liquid hydrocarbon I in the first Fischer-Tropsch synthesis device effluent at least in the interior described catalyzer filtering system of logistics process.The solid content of the first Fischer-Tropsch synthesis device effluent after described process is filtered is less than 50ppm.
The operational condition of the described first Fischer-Tropsch synthesis device is: 180～250 ℃ of temperature of reaction, reaction pressure 1.5～4.0MPa, H/C mol ratio 1.0～3.0, air speed 300～3000h
-1, recycle ratio 1～20.
The catalyzer that the first Fischer-Tropsch synthesis device uses is Fe base fischer-tropsch synthetic catalyst or Co base fischer-tropsch synthetic catalyst.Described catalyzer can be any prior art provide be suitable for Fischer-Tropsch synthetic syrup state bed Fischer Tropsch synthetic catalyst and combination thereof.They can be commercially available commodity, also can adopt any one existing method preparation.
The operational condition of the described second Fischer-Tropsch synthesis device is: 180～250 ℃ of temperature of reaction, reaction pressure 1.5～4.0MPa, H/C mol ratio 1.0～3.0, air speed 300～3000h
-1, recycle ratio 1～20.
The catalyzer that the second Fischer-Tropsch synthesis device uses is Fe base fischer-tropsch synthetic catalyst or Co base fischer-tropsch synthetic catalyst.Described catalyzer can be any prior art provide be suitable for Fischer-Tropsch synthetic fixed bed fischer-tropsch synthetic catalyst and combination thereof.They can be commercially available commodity, also can adopt any one existing method preparation.
Compared with prior art, method provided by the present invention has following beneficial effect:
(1) Fischer-Tropsch synthesis method of two reactors in series of employing, first is a slurry bed ft synthetic reactor, second is fixed bed Fischer-Tropsch synthesis device.Combine slurry attitude bed and be difficult for overtemperature and the simple advantage of fixed bed operation.Contain a certain amount of CH in the paste state bed reactor tail gas
4, CO
2Etc. inertia and low reaction activity gas, can be used as carrier gas and enter fixed-bed reactor, reduced the risk of fixed-bed reactor overtemperatures.
(2) adopt method provided by the invention, can obtain the synthetic fine wax product of fixed bed Fischer-Tropsch.
(3) H is set between the reactor
2Or the function of injecting of CO, distribution that can the flexible reaction product.
Description of drawings
Fig. 1 is the process flow sheet of technical scheme one provided by the invention.
Fig. 2 is the process flow sheet of technical scheme two provided by the invention.
Fig. 3 is the process flow sheet of technical scheme three provided by the invention.
Fig. 4 is the process flow sheet of Comparative Examples 1.
Fig. 5 is the process flow sheet of Comparative Examples 2.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction, but therefore the present invention is not subjected to any restriction.The equipment of many necessity when having omitted industrial application among the figure, as process furnace, pump, valve and interchanger etc., but this is known for a person skilled in the art.
Technical scheme provided by the invention is: the first Fischer-Tropsch synthesis device is a paste state bed reactor, and it adopts the mode of built-in spiral coil cooling tube in the still to move heat.The second Fischer-Tropsch synthesis device is fixed-bed reactor, and it adopts drum heat-obtaining mode to move heat, establishes 6 thermocouples in the fixed-bed reactor and carries out the monitoring of bed axial temperature.
As shown in Figure 1, the technical process of technical scheme one is: the fresh synthesis gas raw material enters paste state bed reactor 2 through pipeline 1 and carries out Fischer-Tropsch synthesis, its reaction product is through after being arranged on strainer 3 filtrations in the paste state bed reactor 2, enter fixed-bed reactor 5 through pipeline 4, carry out further Fischer-Tropsch synthesis.The reaction product of fixed-bed reactor 5 enters high pressure hot separator 7 through pipeline 6 and carries out gas-liquid separation, isolated liquid portion enters thermal low-pressure separators 9 through pipeline 8 and carries out further gas-liquid separation, liquid after the separation, be the high temperature condensation product through pipeline 10 discharge systems, the gas after the separation is through pipeline 24 discharge systems.High pressure hot separator 7 gaseous streams enter cold high pressure separator 12 through pipeline 11 and further carry out gas-liquid separation, the gained liquid stream enters cold low separator 14 through pipeline 13, at this isolating product liquid, be cryogenic condensation thing and water through pipeline 15 discharge systems, gas separated is through pipeline 23 discharge systems.The gaseous stream of cold high pressure separator 12 gained, be that gas II enters compressor 17 through pipeline 16, after boosting, a part is returned paste state bed reactor 2 inlets and fixed-bed reactor 5 inlets respectively through pipeline 19 and pipeline 20, and remaining gas II is through pipeline 22 discharge systems.H
2And/or CO regulates the H/C mol ratio that fixed-bed reactor 5 enter the mouth by pipeline 21.
As shown in Figure 2, the technical process of technical scheme two is: the fresh synthesis gas raw material enters paste state bed reactor 2 through pipeline 1 and carries out Fischer-Tropsch synthesis, after its reaction product is filtered through filter 3, enter high pressure hot separator 5 through pipeline 4 and carry out gas-liquid separation, separating obtained liquid portion enters thermal low-pressure separators 7 through pipeline 6 and carries out further gas-liquid separation, the liquid phase stream of gained, promptly the high temperature condensation product is through pipeline 8 discharge systems, and the gas of gained is through pipeline 33 discharge systems.The gaseous stream of high pressure hot separator 5 enters cold high pressure separator 10 through pipeline 9 and further carries out gas-liquid separation, the liquid stream of gained enters cold low separator 12 through pipeline 11, after further isolating gas, the liquid phase stream of cold low separator 12 gained, be cryogenic condensation thing and water through pipeline 13 discharge systems, gained gas is through pipeline 34 discharge systems.The gaseous stream of cold high pressure separator 10, be that gas I enters fixed-bed reactor 15 through pipeline 14 and carries out Fischer-Tropsch synthesis, the reaction product of fixed-bed reactor 15 enters high pressure hot separator 17 through pipeline 16 and carries out gas-liquid separation, separating obtained liquid stream enters thermal low-pressure separators 19 through pipeline 18, after further isolating gas, the liquid phase stream of thermal low-pressure separators 19 gained, promptly the high temperature condensation product is through pipeline 20 discharge systems, and gained gas is through pipeline 35 discharge systems.The gaseous stream of high pressure hot separator 17 gained enters cold high pressure separator 22 through pipeline 21 and further carries out gas-liquid separation, the liquid stream of cold high pressure separator 22 gained enters cold low separator 24 through pipeline 23, after further isolating gas, the liquid phase stream of cold low separator 24 gained, be cryogenic condensation thing and water through pipeline 25 discharge systems, gas is through pipeline 36 discharge systems.The gaseous stream of cold high pressure separator 22 gained, be that gas II enters compressor 27 through pipeline 26, gas II is after boosting, and a part is returned paste state bed reactor inlet and fixed-bed reactor inlet respectively through pipeline 29 and pipeline 30, and remaining gas II is through pipeline 32 discharge systems.H
2And/or CO regulates the H/C mol ratio that fixed-bed reactor 15 enter the mouth by pipeline 31.
As shown in Figure 3, the technical process of technical scheme three is: the fresh synthesis gas raw material enters paste state bed reactor 2 through pipeline 1 and carries out Fischer-Tropsch synthesis, after its reaction product is filtered through filter 3, enter high pressure hot separator 5 through pipeline 4 and carry out gas-liquid separation, separating obtained liquid portion, be that the high temperature condensation product enters thermal low-pressure separators 7 through pipeline 6, the high temperature condensation product of further isolating gas is through pipeline 8 discharge systems, and gas is through pipeline 34 discharge systems.High pressure hot separator 5 separating obtained gaseous streams enter cold high pressure separator 10 through pipeline 9 and further carry out gas-liquid separation, separating obtained gas stream, and promptly gas I extracts out through pipeline 14.Cold high pressure separator 10 separating obtained liquid streams enter cold low separator 12 through pipeline 11, in cold low separator 12, the minimum gas that flashes off is through pipeline 35 discharge systems, liquid stream is separated into cryogenic condensation thing and water, water is through pipeline 13 discharge systems, and the cryogenic condensation thing mixes with gas I from pipeline 14 through pipeline 33.This mixture flow enters fixed-bed reactor 15 and carries out Fischer-Tropsch synthesis, the reaction product of fixed-bed reactor 15 enters high pressure hot separator 17 through pipeline 16 and carries out gas-liquid separation, separating obtained liquid portion enters thermal low-pressure separators 19 through pipeline 18, after further isolating gas, the liquid phase stream of thermal low-pressure separators 19 gained, be the high temperature condensation product through pipeline 20 discharge systems, gained gas is through pipeline 36 discharge systems.The gaseous stream of high pressure hot separator 17 gained enters cold high pressure separator 22 through pipeline 21 and further carries out gas-liquid separation, separating obtained liquid stream enters cold low separator 24 through pipeline 23, after further isolating gas, the liquid phase stream of cold low separator 24 gained, be cryogenic condensation thing and water through pipeline 25 discharge systems, gained gas is through pipeline 37 discharge systems.The gaseous stream of cold high pressure separator 22 gained, be that gas II enters compressor 27 through pipeline 26, gas II is after boosting, and a part is returned paste state bed reactor inlet and fixed-bed reactor inlet respectively through pipeline 29 and pipeline 30, and remaining gas II is through pipeline 32 discharge systems.H
2And/or CO regulates the H/C mol ratio that fixed-bed reactor 15 enter the mouth by pipeline 31.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
In an embodiment, measure CO in the gaseous product, CH respectively with vapor-phase chromatography
4And C
2-C
4The amount of product, and calculate its mole number.To deduct the amount of the CO that the amount of remaining CO obtains transforming as the amount of the CO of raw material.The mole number that transforms the CO that falls deducts CH in the gaseous product
4And C
2-C
4The mole number of middle C can obtain C
5+The mole number of the C of product.
The CO transformation efficiency refers to react the ratio that the CO quantity of falling accounts for the CO total feed that transforms.CH
4Selectivity refers to generate CH
4Required C mole number accounts for the mole number of the CO that reacts away.C
5+Selectivity refers to generate C
5+The C mole number of product accounts for the mole number of the CO that reacts away.
Syrup state bed Fischer Tropsch synthetic catalyst used in embodiment 1～3 and the Comparative Examples 1 is a cobalt-base catalyst, and it consists of: cobalt contents is 15.2 weight %, and alumina content is 84.8 weight %; Granularity is 95.3% in the particle ratio of 50-80 μ m.Used fixed bed fischer-tropsch synthetic catalyst is a cobalt-base catalyst in embodiment 1～3 and the Comparative Examples 2, and trade names are RFT-2, is produced by catalyzer branch office of China Petrochemical Industry Chang Ling catalyst plant.
Embodiment 1
Present embodiment adopts technical scheme shown in Figure 1, and the reaction product of the first Fischer-Tropsch synthesis device (paste state bed reactor) all enters the second Fischer-Tropsch synthesis device (fixed-bed reactor).
The paste state bed reactor operational condition is: 210 ℃ of temperature, pressure 3.0MPa, reactor inlet H/C mol ratio 2.11.
The fixed-bed reactor operational condition is: 215 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 1.98.
Gas flow is: (the gas volume air speed is 1000h to fresh synthesis gas flow 16.67L/min
-1), reactor 2 circulation gas flow 50.01L/min, reactor 5 circulation gas flow 20.01L/min.
Building-up reactions effect, synthetic oil product distribute and the fixed-bed reactor axial temperature distributes sees Table 1.
Table 1
| The building-up reactions effect | |
| The CO transformation efficiency, mol% | ??88.05 |
| ??CH 4Selectivity, mol% | ??7.03 |
| The C5+ selectivity, mol% | ??86.06 |
| The synthetic oil product distributes | |
| ＜150 ℃ of naphtha fractions, heavy % | ??20.52 |
| 150～320 ℃ of diesel oil distillates, heavy % | ??41.70 |
| The building-up reactions effect | |
| 320～500 ℃ of lubricant base oil fractions, heavy % | ??29.08 |
| ＞500 ℃ of wax distillates | ??8.70 |
| The fixed-bed reactor axial temperature, ℃ | |
| Thermocouple 1 | ??212.2 |
| Thermocouple 2 | ??215.3 |
| Thermocouple 3 | ??218.3 |
| Thermocouple 4 | ??216 |
| Thermocouple 5 | ??214.7 |
| Thermocouple 6 | ??213.3 |
| The axial maximum temperature difference of fixed bed, ℃ | ??6.1 |
Present embodiment adopts technical scheme shown in Figure 2, and the separating obtained gas I of first Fischer-Tropsch synthesis device (paste state bed reactor) reaction effluent enters the second Fischer-Tropsch synthesis device (fixed-bed reactor).
The paste state bed reactor operational condition is: 212 ℃ of temperature, pressure 2.8MPa, reactor inlet H/C mol ratio 2.05.
The fixed-bed reactor operational condition is: 219 ℃ of temperature, pressure 2.8MPa, reactor inlet H/C mol ratio are 2.00.
Gas flow is: (the gas volume air speed is 750h to fresh synthesis gas flow 12.50L/min
-1), reactor 2 circulation gas flow 43.75L/min, reactor 15 circulation gas flow 15.00L/min.
Slurry attitude bed and fixed bed building-up reactions effect, synthetic oil product together distributes and the fixed-bed reactor axial temperature distributes sees Table 2.
Table 2
| The building-up reactions effect | |
| The CO transformation efficiency, mol% | ??93.05 |
| ??CH 4Selectivity, mol% | ??7.35 |
| The building-up reactions effect | |
| The C5+ selectivity, mol% | ??86.72 |
| The synthetic oil product distributes | |
| ＜150 ℃ of naphtha fractions, heavy % | ??22.35 |
| 150～320 ℃ of diesel oil distillates, heavy % | ??43.56 |
| 320～500 ℃ of lubricant base oil fractions, heavy % | ??26.32 |
| ＞500 ℃ of wax distillates | ??7.77 |
| The fixed-bed reactor axial temperature, ℃ | |
| Thermocouple 1 | ??215.7 |
| Thermocouple 2 | ??218.3 |
| Thermocouple 3 | ??222.8 |
| Thermocouple 4 | ??220.6 |
| Thermocouple 5 | ??217.3 |
| Thermocouple 6 | ??216.6 |
| The axial maximum temperature difference of fixed bed, ℃ | ??7.1 |
Present embodiment adopts technical scheme shown in Figure 3, and gas I and cryogenic condensation thing that first Fischer-Tropsch synthesis device (paste state bed reactor) reaction effluent is separating obtained enter the second Fischer-Tropsch synthesis device (fixed-bed reactor).
The paste state bed reactor operational condition is: 212 ℃ of temperature, pressure 3.0MPa, reactor inlet H/C mol ratio 2.02.
The fixed-bed reactor operational condition is: 215 ℃ of temperature, pressure 3.0MPa, reactor inlet H/C mol ratio are 1.92.
Gas flow is: (the gas volume air speed is 500h to fresh synthesis gas flow 8.33L/min
-1), reactor 2 circulation gas flow 33.32L/min, reactor 15 circulation gas flow 11.65L/min.
Slurry attitude bed and fixed bed building-up reactions effect, synthetic oil product together distributes and the fixed-bed reactor axial temperature distributes sees Table 3.
Table 3
| The building-up reactions effect | |
| The CO transformation efficiency, mol% | ??92.63 |
| ??CH 4Selectivity, mol% | ??6.86 |
| The C5+ selectivity, mol% | ??87.07 |
| The synthetic oil product distributes | |
| ＜150 ℃ of naphtha fractions, heavy % | ??18.16 |
| 150～320 ℃ of diesel oil distillates, heavy % | ??41.32 |
| 320～500 ℃ of lubricant base oil fractions, heavy % | ??31.39 |
| ＞500 ℃ of wax distillates | ??9.13 |
| The fixed-bed reactor axial temperature, ℃ | |
| Thermocouple 1 | ??212.9 |
| Thermocouple 2 | ??215.1 |
| Thermocouple 3 | ??217.6 |
| Thermocouple 4 | ??216.4 |
| Thermocouple 5 | ??215.6 |
| Thermocouple 6 | ??214.8 |
| The axial maximum temperature difference of fixed bed, ℃ | ??4.7 |
Comparative Examples 1
This Comparative Examples adopts device flow process shown in Figure 4, is single paste state bed reactor flow process, and paste state bed reactor adopts the mode of built-in spiral coil cooling tube in the still to move heat.
Synthetic gas enters paste state bed reactor 2 through pipeline 1 and carries out Fischer-Tropsch synthesis, after its reaction product is filtered through filter 3, enter high pressure hot separator 5 through pipeline 4 and carry out gas-liquid separation, separating obtained liquid portion enters thermal low-pressure separators 7 through pipeline 6, after further isolating gas, thermal low-pressure separators 7 isolating liquid phase streams, promptly the high temperature condensation product is through pipeline 8 discharge systems, and gained gas is through pipeline 19 discharge systems.High pressure hot separator 5 separating obtained gaseous streams enter cold high pressure separator 10 through pipeline 9 and further carry out gas-liquid separation, the liquid stream of gained enters cold low separator 12 through pipeline 11, after further isolating gas, cold low separator 12 isolating liquid phase streams, be cryogenic condensation thing and water through pipeline 13 discharge systems, gained gas is through pipeline 20 discharge systems.Cold high pressure separator 10 gaseous streams enter compressor 15 through pipeline 14, and gas returns the paste state bed reactor inlet through the rear section of boosting by pipeline 16, pipeline 17, and remaining gas is through pipeline 18 discharge systems.
The paste state bed reactor operational condition is: 210 ℃ of temperature, pressure 2.8MPa, reactor inlet H/C mol ratio 2.08.
Gas flow is: (the gas volume air speed is 500h to fresh synthesis gas flow 4.17L/min
-1), circulation gas flow 12.51L/min.
Building-up reactions effect and synthetic oil product distribute and see Table 4.
Table 4
| The building-up reactions effect | |
| The CO transformation efficiency, mol% | ??92.11 |
| ??CH 4Selectivity, mol% | ??8.09 |
| The C5+ selectivity, mol% | ??84.07 |
| The synthetic oil product distributes | |
| ＜150 ℃ of naphtha fractions, heavy % | ??23.38 |
| 150～320 ℃ of diesel oil distillates, heavy % | ??45.22 |
| 320～500 ℃ of lubricant base oil fractions, heavy % | ??25.30 |
| ＞500 ℃ of wax distillates | ??6.10 |
Comparative Examples 2
This Comparative Examples adopts device flow process shown in Figure 5, is single fixed-bed reactor flow process, adopts drum heat-obtaining mode to move heat.
Synthetic gas enters fixed-bed reactor 2 through pipeline 1, reaction product enters high pressure hot separator 4 through pipeline 3 and carries out gas-liquid separation, the separating liquid part enters thermal low-pressure separators 6 through pipeline 5, after further isolating gas, thermal low-pressure separators 6 isolating liquid phase streams, be the high temperature condensation product through pipeline 7 discharge systems, gained gas is through pipeline 18 discharge systems.The gaseous stream of high pressure hot separator 4 gained enters cold high pressure separator 9 through pipeline 8 and further carries out gas-liquid separation, separating obtained liquid stream enters cold low separator 11 through pipeline 10, after further isolating gas, cold low separator 11 isolating liquid phase streams, be cryogenic condensation thing and water through pipeline 12 discharge systems, gained gas is through pipeline 19 discharge systems.Cold high pressure separator 9 isolating gaseous streams enter compressor 14 through pipeline 13, and gas is after boosting, and part is returned the fixed-bed reactor inlet by pipeline 15 and pipeline 16, and remaining gas is through pipeline 17 discharge systems.
The fixed-bed reactor operational condition is: 215 ℃ of temperature, pressure 3.0MPa, reactor inlet H/C mol ratio 1.98.
Gas flow is: (the gas volume air speed is 1000h to fresh synthesis gas flow 8.34L/min
-1), circulation gas flow 25.02L/min.
Building-up reactions effect and bed axial temperature distribute and see Table 5.
Table 5
| The building-up reactions effect | |
| The CO transformation efficiency, mol% | ??89.23 |
| ??CH 4Selectivity, mol% | ??7.92 |
| The C5+ selectivity, mol% | ??85.65 |
| Axial temperature, ℃ | |
| Thermocouple 1 | ??210.7 |
| Thermocouple 2 | ??214.8 |
| Thermocouple 3 | ??219.3 |
| Thermocouple 4 | ??216.2 |
| Thermocouple 5 | ??215.2 |
| Thermocouple 6 | ??212.5 |
| Axial maximum temperature difference, ℃ | ??8.6 |
By the data of embodiment 1～embodiment 3 and Comparative Examples 2 as can be seen, the axial maximum temperature difference of fixed bed is 4.7～7.1 ℃ among the embodiment, and the axial maximum temperature difference of bed is 8.6 ℃ in the Comparative Examples 2.Hot(test)-spot temperature is obvious in the Comparative Examples, and the risk that occurs overtemperature in operating process is bigger.Therefore, adopt method provided by the invention to carry out Fischer-Tropsch synthesis, can reduce fixed bed overtemperature risk, improve processing safety.
By the data of embodiment 2, embodiment 3 and Comparative Examples 1 as can be seen, under close CO transformation efficiency, it is synthetic to carry out Fischer-Tropsch by method provided by the invention, and during the synthetic oil product distributed,＞500 ℃ of wax distillate content all were higher than single syrup state bed Fischer Tropsch synthesis technique.
Claims (11)
1. a Fischer-Tropsch synthesis method comprises
(1) synthetic gas enters the first Fischer-Tropsch synthesis device, carries out building-up reactions in the first Fischer-Tropsch synthesis device,
(2) all or part of first Fischer-Tropsch synthesis device effluent enters the second Fischer-Tropsch synthesis device and carries out building-up reactions,
(3) the second Fischer-Tropsch synthesis device effluent is separated, is separated into liquid hydrocarbon II, water II and gas II,
(4) step (3) gained gas II is partly discharged, remaining gas II loops back the first Fischer-Tropsch synthesis device and/or the second Fischer-Tropsch synthesis device,
(5) between the first Fischer-Tropsch synthesis device and the second Fischer-Tropsch synthesis device, inject H
2And/or CO, regulating the second Fischer-Tropsch synthesis device ingress H/C mol ratio,
The described first Fischer-Tropsch synthesis device is a paste state bed reactor, and the described second Fischer-Tropsch synthesis device is fixed-bed reactor.
2. in accordance with the method for claim 1, it is characterized in that, the described first Fischer-Tropsch synthesis device effluent separates, and is separated into liquid hydrocarbon I, water I and gas I, and described gas I and optional partially liq hydro carbons I enter the second Fischer-Tropsch synthesis device and carry out building-up reactions.
3. in accordance with the method for claim 1, it is characterized in that the described first Fischer-Tropsch synthesis device is provided with the catalyzer filtering system, comprise liquid hydrocarbon I in the first Fischer-Tropsch synthesis device effluent at least in the interior described catalyzer filtering system of logistics process.
4. in accordance with the method for claim 3, it is characterized in that the solid content of the first Fischer-Tropsch synthesis device effluent after described process is filtered is less than 50ppm.
5. in accordance with the method for claim 1, it is characterized in that the operational condition of the described first Fischer-Tropsch synthesis device is: 180～250 ℃ of temperature of reaction, reaction pressure 1.5～4.0MPa, H/C mol ratio 1.0～3.0, gas hourly space velocity 300～3000h
-1, recycle ratio 1～20.
6. in accordance with the method for claim 1, it is characterized in that the operational condition of the described second Fischer-Tropsch synthesis device is: the H/C mol ratio is 1.0～3.0,180～250 ℃ of temperature of reaction, reaction 1.5～4.0MPa, gas hourly space velocity 300～3000h
-1, recycle ratio 1～20.
7. in accordance with the method for claim 6, it is characterized in that the operational condition of the described second Fischer-Tropsch synthesis device is: the H/C mol ratio is 1.6～2.2.
8. according to claim 1 or 2 described methods, it is characterized in that described gas I or gas II comprise CH
4, C
2H
4, C
2H
6, C
3H
6, C
3H
8, C
4H
8, C
4H
10, H
2, CO, CO
2In one or more.
9. in accordance with the method for claim 2, it is characterized in that described liquid hydrocarbon I comprises cryogenic condensation thing and high temperature condensation product, the final boiling point of described cryogenic condensation thing is not more than 450 ℃.
10. in accordance with the method for claim 9, it is characterized in that the final boiling point of described cryogenic condensation thing is not more than 200 ℃.
11. in accordance with the method for claim 9, it is characterized in that, among the described liquid hydrocarbon I that enters the second Fischer-Tropsch synthesis device, comprise all or part of described cryogenic condensation thing.
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