CN103773410A - Method for improving yield of liquid hydrocarbons - Google Patents
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- CN103773410A CN103773410A CN201210413366.2A CN201210413366A CN103773410A CN 103773410 A CN103773410 A CN 103773410A CN 201210413366 A CN201210413366 A CN 201210413366A CN 103773410 A CN103773410 A CN 103773410A
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Abstract
The invention discloses a method for improving the yield of liquid hydrocarbons. Purified raw synthesis gas enters a first-section Fischer-Tropsch synthesis reactor to react; a first-section Fischer-Tropsch synthesis reaction product is separated in the first-section Fischer-Tropsch synthesis reactor by adopting a slurry bed reactor and an iron-based catalyst; exhaust gas enters a CO2 removal unit; a material flow from which the CO2 is removed is introduced into a second-section reactor; a second-section Fischer-Tropsch synthesis reaction product is separated in the second-section reactor by adopting an enhanced heat transfer fixed bed reactor and a cobalt-based catalyst; part exhaust gas returns to the second-section reactor to react circularly. By the method, the disadvantages that the CO utilization rate is low, the reaction exotherm is difficult to control, the catalyst deactivation rate is high and the like in the conventional process are overcome, and meanwhile, the reaction selectivity and the yield of the liquid hydrocarbons are improved.
Description
Technical field
The present invention relates to a kind of method by hydrogen and carbon monoxide (synthetic gas) gas to liquids, more particularly, is a kind of two stage Fischer-Tropsch synthesis method take synthetic gas as raw material.
Background technology
The method that synthetic gas is converted into liquefied hydrocarbon through katalysis is to be invented by Germany scientist Frans Fischer and Hans Tropsch nineteen twenty-three, and therefore this reaction is named as Fischer-Tropsch synthetic (F-T) reaction.Can produce on a large scale clean fuel (the particularly diesel oil of high-quality) and other high valuable chemicals by Fischer-Tropsch synthesis.Germany conducted a research in the twenties in last century, has realized industrialization, but progressively suffer exit in the rise because of Petroleum Industry after World War II in 1936; South Africa, because the few oil of many coals is subject to again international community's economy and political sanction, forces it to develop the coal liquefaction technology that synthesizes core with Fischer-Tropsch, and has set up the coal-based synthetic oil of First factory in nineteen fifty-five.Twice world oil crisis following 1973 and 1979, Fischer-Tropsch synthetic technology has been aroused the interest of industrialized country again, but plummeting of the World oil price of 1986 caught a cold the extensive industrialization of Fischer-Tropsch synthetic technology again.After entering twentieth century nineties, petroleum resources are shortage and in poor quality increasingly, and coal and Sweet natural gas proven reserve constantly increase, thereby the coal liquefaction take Fischer-Tropsch synthetic technology as core, Sweet natural gas oil-producing technique welcome the peak period of development again, on fischer-tropsch synthetic catalyst and reactor, obtained significant progress, multiple energy enterprises have been set up Sasol and the Dutch Shell company in for example South Africa of large-scale factory.
For low temperature Fischer-Tropsch synthesis, the reactor of industrial employing generally has fixed-bed reactor and two kinds of forms of paste state bed reactor.Fixed-bed reactor feature is simple to operate, and product is easy to collect, and catalyzer is easy to separate with heavy hydrocarbon, and shortcoming is mass transfer and the restriction of receiving reactor types of conducting heat.Paste state bed reactor feature is to adopt catalyst particle, the temperature of reactor is even, thereby there is higher speed of reaction, the pressure drop of bed is less, the replacing of online catalyzer and add very convenient, shortcoming is the problem that has solid-liquid, gas-liquid separation, and catalyst deactivation is fast, needs cyclic regeneration.
For this low temperature Fischer-Tropsch synthesis device of two types, the different improvement method of researchist's invention.CN1281714C discloses the Fischer-Tropsch synthesis method of two sections of paste state bed reactors of a kind of employing, and second segment reactor utilizes the tail gas of first paragraph reactor to react, and two reactor all arranges independent exhaust gas circulation system, and tail gas enters lower carbon number hydrocarbons recovery system.This technique, by reducing the method for single hop reactor CO transformation efficiency, has reduced exothermic heat of reaction amount, and has reduced by product CH
4productive rate, but because ferrum-based catalyst tail gas in comprise a large amount of CO
2, make the inefficiency of circulation of tail gas.
CN1948437A discloses a kind of Fischer-Tropsch synthesis method, adopt the two-part method of slurry state bed and fixed bed combination, after first paragraph reactor, increase decarburization and lower carbon number hydrocarbons conversion system and process tail gas, then enter second segment reactor, the method can be utilized slurry state bed and fixed-bed reactor advantage separately, product structure is flexible, but whole system complicated operation, particularly lower carbon number hydrocarbons conversion system and exhaust gas circulation system, on one anti-and two anti-unstripped gass composition impacts are very large, easily cause unit temp out of control.
CN1736574A has proposed to increase a set of cooling inner tube in fixed-bed reactor reaction tubes, heat-eliminating medium can be in reaction tubes inner tube and reactor enclosure intrastratal flowage heat-obtaining, this scheme can increase heat exchange area, can reduce the radial temperature difference of beds, effectively solve heat transfer problem.But these patents all need fixed-bed reactor to carry out larger change, and the Design and manufacture of reactor can be added to the difficulties, space reactor utilization ratio also declines to some extent.
In addition, thereby also can improve and reach the object of optimizing fixed bed from process aspect, CN1662476A has proposed the method for the synthetic hydrocarbon of a kind of multi-stage fixed-bed reactor, every first stage reactor all add cooling fluid medium be used for absorption reaction produce heat, cooling fluid medium can recycle.The mode of this liquid recirculation can obviously be improved fixed-bed heat transfer, reduces reaction focus and improves reactivity worth.
Summary of the invention
The object of this invention is to provide a kind of two stage Fischer-Tropsch synthesis technique, the method can solve in common process that CO utilization ratio is low, exothermic heat of reaction is difficult to the shortcomings such as control, catalyst deactivation digit rate height, has improved reaction preference and liquid hydrocarbon yield simultaneously.
Method provided by the present invention, comprising:
(1) enter first paragraph Fischer-Tropsch synthesis device through the material synthesis gas purifying and react, described first paragraph Fischer-Tropsch synthesis device is paste state bed reactor, and adopts ferrum-based catalyst;
(2) separate first paragraph Fischer-Tropsch synthesis product, tail gas I enters de-CO
2unit, removes CO
2after logistics import second segment Fischer-Tropsch synthesis device;
(3) second segment Fischer-Tropsch synthesis device is fixed-bed reactor, and adopts cobalt-base catalyst;
(4) separate second segment Fischer-Tropsch synthesis product, partial tail gas II returns to second segment Fischer-Tropsch synthesis device circulating reaction, residual exhaust II discharge.
The synthetic gas that material synthesis gas in step (1) is preferably prepared by gasification, generally comprises the critical process processes such as gasification, conversion, purification.H in material synthesis gas
2with the volume ratio of CO be 0.66～2.2, be preferably 1.0～1.8.
The reaction conditions of first paragraph Fischer-Tropsch synthesis device in step (1): working pressure 1.0～5.0MPa, be preferably 2.0～4.0MPa, 150～300 ℃ of temperature of reaction, are preferably 190～250 ℃, and the gas hourly space velocity of fresh synthesis gas raw material is 200～2000h
-1, be preferably 400～1500h
-1.
Described in step (1), ferrum-based catalyst contains Fe, Cu, SiO
2, and alkaline-earth metal and/or K, described ferrum-based catalyst size-grade distribution is 50 ~ 100 μ m.Preferably, described ferrum-based catalyst weight ratio is 100Fe:5Cu:5K:25SiO
2.
In step (2) by the CO in tail gas I
2remove, adopt conventional removal methods, the de-CO of for example hot salt of wormwood
2method, and by CO in tail gas I
2content takes off to volume content below 1%.
In step (3), fixed-bed reactor adopt calandria type fixed bed reactor, the reaction tubes of described calandria type fixed bed reactor respectively by reactor upper tubesheet and reactor lower tubesheet stationary arrangement in reactor shell, the tube wall of described reaction tubes is made up of porous surface layer and smooth surface layer.
The surface of contact cooling medium is porous surface layer, and the surface of contact catalyst is smooth surface layer.If catalyst loading is in reaction tubes, the outside surface of described reaction tubes tube wall is porous surface layer, and internal surface is smooth surface layer.Heat-eliminating medium flows through reactor enclosure journey takes the heat of reaction generation out of reactor, and traverse baffle is distributed in the middle of reactor according to a determining deviation.
The thickness of the porous surface layer of described reaction tubes tube wall is 0.1 ~ 0.5mm, described porous surface layer is uniformly distributed multiple apertures, aperture can be regular figure, also can be irregular figure, its effective aperture is 0.02 ~ 0.5mm, and open area ratio is 50% ~ 80%, and the thickness of preferred described porous surface layer is 0.2 ~ 0.4mm, effective aperture is 0.05 ~ 0.4mm, and open area ratio is 55% ~ 75%.Described open area ratio refers to, take the outer surface area in atresia situation as benchmark, all aperture area sums account for the ratio of the outer surface area of integral surface layer.
The thickness of described smooth surface layer is 1 ~ 8mm.
Described reaction tubes can adopt any modes such as sintering, spraying, plating and mechanical workout to manufacture.
Described porous surface layer is alloy material, is selected from one or more of Fe, Ni, Cr, Mo, Mn, Ti, Cu, W, V, Nb metal, and comprises one or more in other non-metallic element P, S, C, Si that has promoter action.
Described fixed-bed reactor are calandria type fixed bed reactor, are arranged with 100～10000 reaction tubess in reactor, and the interior diameter of every reaction tubes is 20～60mm, is preferably 25～50mm, and length is 4～15m, is preferably 6～12m.
Described step (3) Co based Fischer-Tropsch synthesis catalyst, in oxide compound, cobalt metal component mass content is 1%～60%.Co based Fischer-Tropsch synthesis catalyst is evenly seated in every reaction tubes, Co based Fischer-Tropsch synthesis catalyst granularity (diameter) is 0.5～5mm, be preferably 1～3mm, the shape of Co based Fischer-Tropsch synthesis catalyst can be column, spherical, hollow ball, ring-type, saddle, trilobal cross bar, four blade profile bars etc.
Second segment Fischer-Tropsch synthesis condition is: working pressure 1.0～5.0MPa, be preferably 2.0～4.0MPa, and 150～300 ℃ of temperature of reaction, are preferably 190～250 ℃, and the gas hourly space velocity of raw material of synthetic gas is 200～2000h
-1, be preferably 400～1500h
-1, recycle ratio is 1～5, is preferably 2～3.
It can be the reactor of multiple equal forms single or in parallel at first paragraph of the present invention and second segment reactor.
In the method for the invention implementation process, can be by adjusting the processing condition properly distributed reaction load of each section of reaction.Preferably CO+H in first paragraph Fischer-Tropsch synthesis device
2conversion rate control more than 60%.
Preferably adopt one-pass reaction process at first paragraph paste state bed reactor of the present invention, do not need circulation of tail gas, but also certain internal circulating load can be set as required.Described second segment fixed-bed reactor adopt the flow process of partial tail gas circulation, and recycle ratio is 1～5, is preferably 2～3.
The present invention compared with prior art, have the following advantages: by carrying out the method for two reactor operation, paste state bed reactor and fixed-bed reactor combination, the combination of ferrum-based catalyst/cobalt-base catalyst, give full play to the advantage separately of slurry state bed and fixed-bed reactor, and the advantage that ferrum-based catalyst anti-sulfur poisonous performance is strong, water-gas shift ability is strong, and combine the high advantage of cobalt-base catalyst heavy hydrocarbon yield.Adopt technology of the present invention, had the feature of two class catalyst prods concurrently, can produce according to market demands the raw material of petroleum naphtha, solvent oil, kerosene, diesel oil, base oil and extraordinary paraffin.
Adopted the fixed-bed reactor with porous surface layer reaction tubes at second segment, tube side-shell side conducts heat and has obtained strengthening, has solved the problem that existing fixed-bed reactor are axial, radial symmetry gradient is large; Can adopt less circulation of tail gas amount, significantly reduce reactor pressure decrease; Eliminate focus in reactor, catalyst operation and product result are optimized significantly.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet of the method for synthin provided by the invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further described, but therefore the present invention is not subject to any restriction.In figure, omitted many utility appliance, as interchanger, pump, control valve etc., but this is known to those of ordinary skills.
Synthetic gas (hydrogen and the carbon monoxide) unstripped gas 1 through purifying attracting from coal gasification unit imports from the first reactor 2 bottoms, enter in the paste state bed reactor 2 that iron-base fischer-tropsch synthesis catalyst is housed through gas distributor, Fischer-Tropsch synthesis occurs after contacting with catalyzer, and 41 is the cooling system of reactor 2.Reaction produce resultant through filter 3 realize with catalyzer separate and derive reactive system.The synthetic gas (tail gas I) not ruing out of is derived from reactor top with lightweight reaction product 4, enters an anti-high-pressure separator 5 and carries out gas-liquid separation.Unreacted synthetic gas and gas-phase product are derived from the top of an anti-high-pressure separator 5, enter the de-CO of hot salt of wormwood
2reactive system 6, removes contained CO
2.Synthetic oil is derived from anti-high-pressure separator 5 bottoms, enters light pressure separator 20 through pipeline 7, and the waste water of generation is directed at oxygenatedchemicals recovery system through pipeline 8.De-CO
2after gas 9 enter the second reactor 10 from top, contact with Co based Fischer-Tropsch synthesis catalyst after occur Fischer-Tropsch synthesis, 42 is the cooling system of reactor 10.The synthetic gas (tail gas II) not ruing out of is derived from reactor 10 bottoms with reaction product 11, enters two anti-high pressure hot separators 12 and carries out gas-liquid separation.Synthetic wax 14 is derived from high pressure hot separator 12 bottoms, enters thermal low-pressure separators 22, and at the isolated heavy synthetic oil 35 of thermal low-pressure separators 22, coal mine gas enters gas pipeline 32.The product of unreacted synthetic gas and not liquefaction is derived from the top of two anti-high pressure hot separators 12, enter cold high pressure separator 13 and carry out gas-liquid separation, gaseous component 15 is derived rear most of gas 16 and is mixed with unstripped gas as circulation gas Returning reactor entrance 18 via compressor 17 superchargings, and partial tail gas 31 enters tail gas pipe network.Cold high pressure separator 13 separates and obtains liquid phase stream 19 and enter cold low separator 20 and carry out oily water separation again, separating obtained synthetic oil 33 guiding systems, it is 34 to be directed at oxygenatedchemicals recovery system that the isolated water of cold low separator 20 and high-pressure separator 5, the isolated water 21 of cold high pressure separator 13 converge, and the isolated gas of cold low separator 20 and the isolated gas of thermal low-pressure separators 22 enter gas pipeline 32.
Below in conjunction with embodiment, method of the present invention is illustrated further, but not thereby limiting the invention.
Embodiment
The present embodiment adopts flow process shown in accompanying drawing and device to carry out Fischer-Tropsch synthesis.Paste state bed reactor adopts slurry outside circulation unpack format.Fixed-bed reactor are that shell-and-tube reactor adopts 300 interior diameter 32mm reaction tubess, and porous surface layer is ferroalloy powder (Fe80Ni18P2), adopts sintering process manufacture, porous surface layer thickness 0.3mm, open area ratio 60%, effective aperture 0.07mm, the thickness of smooth surface layer is 3mm.
First paragraph reactor adopts iron-base fischer-tropsch synthesis catalyst, and catalyzer is prepared by the precipitator method, and chief component is Fe, Cu, alkaline-earth metal, K and SiO
2, described catalyst weight consists of 100Fe:5Cu:5K:25SiO
2.The preparation process of catalyzer used is as follows: by the mixed solution of a certain proportion of iron nitrate and cupric nitrate and Na
2cO
3co-precipitation continuously under the condition that the aqueous solution is 10 at 70 ℃, pH, the filter cake that precipitation obtains after the processes such as filtration, washing mixes with potassium silicate solution, after the making beating of washing and filtering, filter cake, the spray-dried size range that obtains is at the granules of catalyst of 50～100 microns, and catalyzer can be replaced into reactor and use after reduction is processed.
In the second reactor reaction pipe, load Co/Al
2o
3catalyzer.The preparation process of catalyzer used is as follows: get aluminum oxide powder, drip distilled water to just wetting, write down the volume that consumes water, then calculate by cobalt contents (oxide compound) 27 % by weight, make Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES steeping fluid.Then with this solution impregnation aluminum oxide to just wetting, leave standstill 8 hours, then in 120 ℃ dry 4 hours, in muffle furnace, 450 ℃ of roastings make catalyzer for 4 hours.Size range 0.8～the 1.2mm of gained Co based Fischer-Tropsch synthesis catalyst.Catalyzer need to reduce processing before use in atmosphere of hydrogen.
Unstripped gas is synthesis gas from coal gasification, wherein H
2, the shared volume ratio of CO is greater than 99%, all the other are CH
4, CO
2, N
2deng rare gas element.H
2with CO volume ratio be 1.6.CO+H in first paragraph Fischer-Tropsch synthesis device
2transformation efficiency be 65%.
Separate first paragraph Fischer-Tropsch synthesis product, tail gas I enters de-CO
2unit, by CO in tail gas I
2content takes off to volume content 0.8%.Remove CO
2after tail gas I import second segment Fischer-Tropsch synthesis device, under cobalt-base catalyst effect, react.Separate second segment Fischer-Tropsch synthesis product, partial tail gas II returns to second segment Fischer-Tropsch synthesis device circulating reaction, residual exhaust II discharge.
The processing condition of device are listed in table 1.
The processing condition that table 1 installs
| Processing condition | First step reactor | Second stage reactor |
| Temperature, ℃ | 245 | 210 |
| Pressure, MPa | 3.1 | 2.5 |
| Gas hourly space velocity, h -1 | 1000 | 3000 |
| Circulation gas and feed gas volume ratio | / | 2.5 |
Under above-mentioned processing condition, synthetic gas total conversion rate reaches 95%, and methane overall yield is lower than 5%, C
5 +hydro carbons productive rate is 88%, and oily yield is 185g/m
3synthetic gas, in hydrocarbon liquid phase series products, the above cut yield of kerosene can reach 80%.
Comparative example
Adopt two sections of Fischer-Tropsch synthesis methods, two reactor is paste state bed reactor, and uses ferrum-based catalyst, and the tail gas of first paragraph reactor is as the unstripped gas of second segment reactor, and every section of reactor arranges independently exhaust gas circulation system.Unstripped gas is synthesis gas from coal gasification, wherein H
2, the shared volume ratio of CO is greater than 99%, all the other are CH
4, CO
2, N
2deng rare gas element.H
2with CO volume ratio be 1.54.The processing condition of device are listed in table 2.
The processing condition that table 2 installs
| Processing condition | First step reactor | Second stage reactor |
| Temperature, ℃ | 235 | 235 |
| Pressure, MPa | 3.0 | 2.5 |
| Gas hourly space velocity, h -1 | 5000 | / |
| Circulation gas and feed gas volume ratio | 0.2 | 1 |
Under above-mentioned processing condition, synthetic gas total conversion rate reaches 92%, and methane overall yield is lower than 5%, C
5 +hydro carbons productive rate is 78%, oily yield 170g/m
3synthetic gas, in hydrocarbon liquid phase series products, the above cut yield of kerosene is 65%.
Claims (17)
1. a method that improves liquid hydrocarbon yield, comprises the following steps:
(1) enter first paragraph Fischer-Tropsch synthesis device through the material synthesis gas purifying and react, described first paragraph Fischer-Tropsch synthesis device is paste state bed reactor, and adopts ferrum-based catalyst;
(2) separate first paragraph Fischer-Tropsch synthesis product, tail gas I enters de-CO
2unit, removes CO
2after logistics import second segment Fischer-Tropsch synthesis device;
(3) second segment Fischer-Tropsch synthesis device is fixed-bed reactor, and adopts cobalt-base catalyst;
(4) separate second segment Fischer-Tropsch synthesis product, partial tail gas II returns to second segment Fischer-Tropsch synthesis device circulating reaction, residual exhaust II discharge.
2. in accordance with the method for claim 1, it is characterized in that H in the described material synthesis gas of step (1)
2with the volume ratio of CO be 0.66～2.2.
3. in accordance with the method for claim 1, it is characterized in that, step (2) is by CO in tail gas I
2content takes off to volume content below 1%.
4. in accordance with the method for claim 1, it is characterized in that, the described fixed-bed reactor of step (3) are calandria type fixed bed reactor, and the tube wall of its reaction tubes is made up of porous surface layer and smooth surface layer.
5. in accordance with the method for claim 4, it is characterized in that, the thickness of the porous surface layer of described reaction tubes tube wall is 0.1 ~ 0.5mm, and effective aperture is 0.02 ~ 0.5mm, and open area ratio is 50% ~ 80%; The thickness of smooth surface layer is 1 ~ 8mm.
6. in accordance with the method for claim 4, it is characterized in that, the thickness of the porous surface layer of described reaction tubes tube wall is 0.2 ~ 0.4mm, and effective aperture is 0.05 ~ 0.4mm, and open area ratio is 55% ~ 75%.
7. according to the method described in claim 1 or 4, it is characterized in that, in described fixed-bed reactor, be arranged with 100～10000 reaction tubess, the interior diameter of every reaction tubes is 20～60mm, and length is 4～15m.
8. in accordance with the method for claim 7, it is characterized in that, the interior diameter of described reaction tubes is 25～50mm, and length is 6～12m.
9. in accordance with the method for claim 4, it is characterized in that, described porous surface layer is alloy material, be selected from one or more of Fe, Ni, Cr, Mo, Mn, Ti, Cu, W, V, Nb metal, and comprise one or more in other non-metallic element P, S, C, Si that has promoter action.
10. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of first paragraph Fischer-Tropsch synthesis device, pressure 1～5MPa, 150～300 ℃ of temperature, the gas hourly space velocity of fresh synthesis gas raw material is 200～2000h
-1.
11. in accordance with the method for claim 10, it is characterized in that the reaction conditions of first paragraph Fischer-Tropsch synthesis device: pressure 2.0～4.0MPa, and 190～250 ℃ of temperature, the gas hourly space velocity of fresh synthesis gas raw material is 400～1500h
-1.
12. in accordance with the method for claim 1, it is characterized in that, described ferrum-based catalyst contains Fe, Cu, SiO
2, and alkaline-earth metal and/or K, described ferrum-based catalyst size-grade distribution is 50 ~ 100 μ m.
13. in accordance with the method for claim 12, it is characterized in that, described ferrum-based catalyst weight ratio is 100Fe:5Cu:5K:25SiO
2.
14. in accordance with the method for claim 1, it is characterized in that CO+H in first paragraph Fischer-Tropsch synthesis device
2conversion rate control more than 60%.
15. in accordance with the method for claim 1, it is characterized in that, in described step (3), second segment Fischer-Tropsch synthesis condition is: pressure 1～5MPa, and 150～300 ℃ of temperature, the gas hourly space velocity of raw material of synthetic gas is 200～2000h
-1, recycle ratio is 1～5.
16. in accordance with the method for claim 1, it is characterized in that, in described step (3), second segment Fischer-Tropsch synthesis condition is: reaction pressure 2～4MPa, and temperature is 190～250 ℃, the gas hourly space velocity of raw material of synthetic gas is 400～1500h
-1, recycle ratio is 2～3.
17. in accordance with the method for claim 1, it is characterized in that, described step (3) Co based Fischer-Tropsch synthesis catalyst, and in oxide compound, cobalt metal component mass content is 1%～60%, granularity is 0.5～5mm.
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|---|---|---|---|---|
| CN105154125A (en) * | 2015-07-10 | 2015-12-16 | 北京宝塔三聚能源科技有限公司 | Conversion technology for combined production of methane, paraffin and high carbon olefin from synthetic gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948437A (en) * | 2006-10-08 | 2007-04-18 | 神华集团有限责任公司 | Fischer-Tropsch synthesis method |
| CN101329146A (en) * | 2008-07-17 | 2008-12-24 | 华东理工大学 | Porous surface U type heat exchange tube |
| CN101863728A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948437A (en) * | 2006-10-08 | 2007-04-18 | 神华集团有限责任公司 | Fischer-Tropsch synthesis method |
| CN101329146A (en) * | 2008-07-17 | 2008-12-24 | 华东理工大学 | Porous surface U type heat exchange tube |
| CN101863728A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154125A (en) * | 2015-07-10 | 2015-12-16 | 北京宝塔三聚能源科技有限公司 | Conversion technology for combined production of methane, paraffin and high carbon olefin from synthetic gas |
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