CN100575457C - A kind of Fischer-Tropsch synthesis method - Google Patents
A kind of Fischer-Tropsch synthesis method Download PDFInfo
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- CN100575457C CN100575457C CN200610140019A CN200610140019A CN100575457C CN 100575457 C CN100575457 C CN 100575457C CN 200610140019 A CN200610140019 A CN 200610140019A CN 200610140019 A CN200610140019 A CN 200610140019A CN 100575457 C CN100575457 C CN 100575457C
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Abstract
A kind of Fischer-Tropsch synthesis method may further comprise the steps: (1) makes the producing synthesis gas from coal raw material enter first step Fischer-Tropsch synthesis device, contacts, reacts with ferrum-based catalyst; (2) separate the first order reaction product, the remaining tail gas in reaction back removes CO
2After, enter C1-C4 hydrocarbon conversion device to produce CO and H
2, make the tail gas after the conversion enter second stage Fischer-Tropsch synthesis device then, contact, react with cobalt-base catalyst; (3) separate the second order reaction product, discharge section tail gas, remaining tail gas return first step Fischer-Tropsch synthesis device and recycle.This method can be adjusted the reaction depth between the I and II, regulates the purpose product structure neatly, the strain market requirement.
Description
Technical field
The present invention relates to a kind of Fischer-Tropsch synthesis method, more particularly, be a kind of be the two-stage Fischer-Tropsch synthesis method of raw material with the coal based synthetic gas.
Background technology
Along with oil price is constantly soaring in recent years, people more and more pay attention to the technology that Development and Production substitutes oil product.With coal, Sweet natural gas or other biomass is raw material, synthesizes core technology with Fischer-Tropsch and produces high-quality eco-friendly oil product, becomes present research focus.The characteristics of the energy structure of China are that the coal heavy wool is few, and the technology that with the coal is raw material generation oil product is one of strategy of China's reply oil shortage, as seen develops coal system oil tech and has urgency and feasibility in China.
Up to the present, having succeeded in developing iron system and cobalt is the Fischer-Tropsch synthesis process of two class catalyzer.Wherein the Fe-series catalyst activity is relatively low, but fischer-tropsch synthetic catalyst poisonous substance abilities such as anti-sulphur are strong, and the chainpropagation probability of Fischer-Tropsch synthesis has more light olefin, naphtha fraction in the product about 0.7, and diesel oil distillate and wax phase are to few; Cobalt series catalyst is active high, but antitoxin thing ability a little less than, the chainpropagation probability can reach more than 0.9, is mainly diesel oil distillate and wax in the product.
Because producing synthesis gas from coal contains the fischer-tropsch synthetic catalyst poisonous substance of more kind, it is generally acknowledged that the Fischer-Tropsch that has only ferrum-based catalyst just to can be used for producing synthesis gas from coal is synthetic, and that Fischer-Tropsch composite reactive and the better cobalt-base catalyst of middle runnings selectivity are difficult to be applied to the Fischer-Tropsch of producing synthesis gas from coal is synthetic.How in the Fischer-Tropsch synthesis that with the producing synthesis gas from coal is raw material, to use cobalt series catalyst, make Fischer-Tropsch synthesis process become very flexible, improve the productive rate of oil product, and can be according to different demands to produce alkene or, the production technology of developing coal system oil to be had very important significance to produce intermediate oil.
CN1611565A discloses a kind of technology of producing liquid fuel with synthetic gas, and this processing method comprises that Fischer-Tropsch synthesis unit, C3-C5 reclaim unit, three parts of refinery unit.Wherein the Fischer-Tropsch synthesis unit is divided into two-stage, and product is paraffin and condensation product; Two-stage Fischer-Tropsch synthesizer carries out the circulation of part tail gas respectively; The residual exhaust of first step Fischer-Tropsch synthetic gas enters second stage Fischer-Tropsch synthesizer as unstripped gas; The residual exhaust of second stage Fischer-Tropsch synthesizer enters into C3-C5 and reclaims the unit.It is by degree of depth refrigerative method that C3-C5 reclaims the unit, reclaims the above component of C3 of the overwhelming majority in the tail gas, and the paraffin and the condensation product of these components and the production of two-stage Fischer-Tropsch synthesis unit enter the production that refinery unit is carried out liquid fuel together.This process using dual stage apparatus Fischer-Tropsch is synthetic, can reduce CH by reducing the method for single-stage CO transformation efficiency
4Productive rate, but the tail gas of first step device directly advances secondary Fischer-Tropsch synthesizer, the CO that first step Fischer-Tropsch synthesizer generates
2Know from experience with indifferent gas such as methane and in the device of the second stage, to gather, cause in actually operating, will keeping operation with the concentration that reduces rare gas element in the device recycle gas of the second stage, reduced the economy of whole technology by strengthening second stage device exhaust quantity discharged.
Summary of the invention
The objective of the invention is to: a kind of new coal-based Fischer-Tropsch synthesis method is provided,, tackles the variation of the market requirement flexibly so that improve the oil product yield, diversify.
Coal-based Fischer-Tropsch synthesis method provided by the present invention may further comprise the steps:
(1) makes the producing synthesis gas from coal raw material enter first step Fischer-Tropsch synthesis device, contact with ferrum-based catalyst, and under the Fischer-Tropsch synthesis condition, react;
(2) separate the first order reaction thing, the remaining tail gas in reaction back removes CO
2After, enter C1-C4 hydrocarbon conversion device to produce CO and H
2, make the tail gas after the conversion enter second stage Fischer-Tropsch synthesis device then, contact with cobalt-base catalyst, and under the Fischer-Tropsch synthesis condition, react;
(3) separate the second order reaction product, discharge section tail gas, remaining tail gas return first step Fischer-Tropsch synthesis device and recycle.
Further describe coal-based Fischer-Tropsch synthesis method of the present invention below, but therefore the present invention is not subjected to any restriction.
In the method for the invention, be raw material with the producing synthesis gas from coal.This synthetic gas at first through purifying the material to the toxic effect of fischer-tropsch synthetic catalyst such as the sulphur remove in the producing synthesis gas from coal to be contained, makes it to satisfy substantially the service requirements of ferrum-based catalyst.Wherein, H in the described producing synthesis gas from coal
2Be generally 1.2-2.2 with the volume ratio of CO, preferred volume ratio is 1.4-1.8.
In the method for the invention, described Fischer-Tropsch synthesizer comprises two-stage, and wherein the first step preferably adopts paste state bed reactor, and fixed-bed reactor are preferably adopted in the second stage.The reactor of described first step Fischer-Tropsch synthesizer can be the paste state bed reactor of a paste state bed reactor or a plurality of parallel connections; The fixed-bed reactor of fixed-bed reactor or a plurality of parallel connections can be established in the second stage.In described first step paste state bed reactor, adopt ferrum-based catalyst, for example, adopt the Fe-series catalyst of the precipitator method commonly used or coprecipitation method preparation.In the fixed-bed reactor of the described second stage, adopt cobalt-base catalyst, for example, adopt the cobalt catalyst of immersion process for preparing commonly used.
In first step Fischer-Tropsch synthesis device of the present invention, reaction pressure is 15-55Bar, preferred 25-40bar; Temperature of reaction is 180-280 ℃, is preferably 210-250 ℃.In the Fischer-Tropsch synthesis device of the second stage, reaction pressure is 10-50bar, is preferably 15-30bar; Temperature of reaction is 150-280 ℃, and preferred temperature is 190-230 ℃.Therefore, as can be seen, the invention belongs to low temperature Fischer-Tropsch synthesis process; Fresh feed gas is 300-3000Nm with the gas agent ratio of catalyzer
3/ m
3, preferred 500-1500Nm
3/ m
3, the ratio of circulating flow rate and fresh tolerance is at 1-5, preferred 2-3.
In the implementation process of the method for the invention, can be by adjusting the first step and partial processing parameter, properly distributed CO+H
2Transformation efficiency.For example, the transformation efficiency of the control first step is lower, makes most CO+H
2In the reactor of the second stage, be converted into hydro carbons, farthest to bring into play the effect of cobalt catalyst.Generally speaking, CO+H in first step reactor
2Transformation efficiency preferably be controlled at below 50%.
In the method for the invention, the described ratio of returning process tail gas that first step Fischer-Tropsch synthesis device recycles and fresh producing synthesis gas from coal raw material, i.e. recycle ratio, can adjust within the specific limits, for example, described recycle ratio can be 1-5, and preferred recycle ratio is 2-3.
In the method for the invention, be arranged at the CO that is used for removing first step reactor tail gas (one-level tail gas) between first step reactor and the second stage reactor
2Device, can adopt the CO that removes commonly used
2Processing method, for example, hot salt of wormwood takes off CO
2Technology etc. are preferably with CO in the one-level tail gas
2Concentration reduce to below 1% (volume).
In the method for the invention, be arranged at device that the hydrocarbon gas such as methane that are used between first step reactor and the second stage reactor first step reactor tail gas are converted into synthetic gas and can utilize the processing method of sophisticated Sweet natural gas preparing synthetic gas, for example natural gas auto-thermal oxidation preparing synthetic gas method etc.
The main products of Fischer-Tropsch synthesizer of the present invention production is hydrocarbon gas (containing low-carbon alkene), light naphthar and heavy naphtha, diesel oil distillate, wax and oxygenatedchemicals, is many with petroleum naphtha, diesel oil distillate and wax especially.
In the method for the invention, the wax of producing in the Fischer-Tropsch synthesis device passes through to discharge as product after interior strainer that is provided with of device and the catalyst separating.
Isolate high temperature condensation product, cryogenic condensation thing, the reaction water that contains oxygenatedchemicals and tail gas from the reactor head expellant gas through the high and low temperature separator.Wherein, the service temperature of low-temperature separator preferably can not be higher than 50 ℃, and its service temperature is low more good more.
Compared with prior art, coal-based Fischer-Tropsch synthesis method provided by the present invention has following beneficial effect:
Because Fischer-Tropsch synthesis method of the present invention adopts Fe-series catalyst in first step fischer-tropsch reactor, not only play the effect of catalysis Fischer-Tropsch synthesis process, remove the catalyzer poison in the fresh feed gas simultaneously,, improve the H in the unconverted synthesis gas by catalytic water shift conversion reaction
2/ CO ratio, the quality of raising first step tail gas makes it to meet the service requirements of second stage cobalt series catalyst.Simultaneously, setting removes CO between I and II
2Facility and make C1-C4 be converted into the facility of synthetic gas, with the further composition that improves second stage charging.In the fischer-tropsch reactor of the second stage, adopt cobalt series catalyst, give full play to the characteristics of cobalt series catalyst, improve the distribution of product, improve the oil product yield.The major part of second stage reaction end gas loops back the inlet of first step reactor, a small amount of discharge, thus improve CO+H
2Utilization ratio.
Just because of compound iron catalyst and the cobalt catalyst of having used of the method for the invention, make and in a cover Fischer-Tropsch synthesizer, can produce the product that has two class catalyzer characteristics concurrently, increased product category, had stronger adaptibility to response for the produce market changes in demand.
The present invention adjusts the processing parameter of I and II, properly distributed CO+H
2Transformation efficiency, control one-level transformation efficiency is lower, most CO+H
2Turn to hydro carbons by two counter-rotatings, farthest bring into play the effect of cobalt catalyst, the production middle runnings of maximum ground.Also can improve the severity of first order reaction, improve CO+H
2The transformation efficiency in one-level, produce alkene and naphtha fraction more.
Description of drawings
Fig. 1 is the schematic flow sheet of Fischer-Tropsch synthesis method of the present invention.
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.For outstanding process thought of the present invention, the complementary equipment of having used always when having omitted industrial application among the figure is as process furnace, pump, valve and interchanger etc.
As shown in Figure 1, the fresh coal based synthetic gas 1 through purifying and adjust hydrogen-carbon ratio is mixed into unstripped gas 2 with circulation gas 12 through recycle compressor 107 superchargings.Unstripped gas 2 through interchanger 105 and 103 and the Fischer-Tropsch synthetic heat exchange after, enter reactor 102, Fischer-Tropsch synthesis takes place under the effect of the synthetic iron catalyst of Fischer-Tropsch.Because Fischer-Tropsch synthesis is strong exothermal reaction, adopt steam coils that reaction heat is taken out, the temperature of whole reactor 102 is by the pressure-controlling of steam pockets 101, by-product water vapor 26.The wax that generates obtains product wax 13 by built-in strainer and the catalyst separating of reactor, goes out device as product.The mixture 3 of the lighting end in reacted unstripped gas and the part Fischer-Tropsch synthetic comes out from the top of reactor 102, after interchanger 103 heat exchange, deliver to hot high score 104 with unstripped gas and carry out gas-liquid separation, isolate hot high score product 11 and hot high score gas 4, hot high score gas 4 again with the unstripped gas heat exchange after, fall within the range of about 50 ℃, enter cold high score 106 then and carry out gas-liquid separation, isolate cold high score product 6 and tail gas 5, the tail gas 5 of discharging from cold high score top is through taking off CO
2Device 108 removes CO
2After, enter hydrocarbon conversion device 109, be CO+H with the C1-C4 hydrocarbon conversion
2From all gas logistics 33 of hydrocarbon conversion device through secondary heat exchanger 115 and 113 and 43 heat exchange of secondary Fischer-Tropsch process exhaust after, enter secondary Fischer-Tropsch synthesis device 112 from the top.The same with one-level Fischer-Tropsch synthesis device, the temperature of reaction of secondary Fischer-Tropsch synthesis device is by steam pockets 111 controls, and richness is produced water vapor 25.After flow through after coming out in second reactor bottom interchanger 113 and unstripped gas heat exchange, carry out gas-liquid separation at the resulting product 43 of secondary Fischer-Tropsch synthesis under the effect of cobalt catalyst, isolate hot high score product 37 and hot high score gas 34 at hot high score 114.Hot high score gas 34 again with the unstripped gas heat exchange after, fall within the range of about 50 ℃, enter cold high score 116 and carry out gas-liquid separation, isolate cold high score product 36 and cold high score gas 35.According to the content of rare gas elementes such as methane in 35, determine the quantity discharged of tail gas 38, remaining tail gas mixes with fresh feed gas after the recycle compressor supercharging, returns the A reactor inlet.After the cold high score product 6 of I and II and 36 mixes, enter cold low branch 118 again with after the low branch of heat gas 39 mixes, be separated into generation water 68, the synthetic cold low minute product 58 of Fischer-Tropsch and cold low minute gas 48 of containing oxygenatedchemicals and go out device.Enter after the hot high score product 37 of I and II and 40 mixes that heat is low divides 117 to be separated into low product 78 and the low gas 39 that divides of heat of dividing of heat, wherein 78 go out device as product, the low gas 39 that divides of heat mixes with cold high score product after lowering the temperature.
The following examples will further specify processing method provided by the present invention, but therefore the present invention is not subjected to any restriction.
Embodiment 1
Present embodiment adopts technical process shown in Figure 1, after fresh feed gas is gasification, obtains H through purification and water-gas shift
2/ CO volume ratio is 1.5 synthetic gas, and concrete composition sees Table 1.
The composition of table 1 coal based synthetic gas raw material
| Composition, v% | Ratio |
| CO | 39.81 |
| H 2 | 59.74 |
| CO 2 | 0.08 |
| Ar | 0.05 |
| CH 4 | 0.08 |
| N 2 | 0.24 |
The weight of Fe-series catalyst that A reactor adopts consists of 100Fe: 5Cu: 5K
2O: 25SiO
2Its preparation method is made into mixing solutions for earlier iron nitrate and copper nitrate solution being mixed in proportion, and is heated to the boiling back and adds Na
2CO
3Solution precipitates, and filters and wash alkali-free then; With the filter cake making beating, add excessive K
2SiO
3, and add HNO
3Unnecessary potassium ion is washed off, washing and filtering, the spray-dried granules of catalyst that obtains size range at the 60-90 micron in filter cake making beating back, catalyzer can be used as qualified Fe-series catalyst and uses after reduction.
The weight of the cobalt catalyst that second reactor adopted consists of 15Co: 5Zr: 100Al
2O
3Its preparation method is used rotary drum dehydration by evaporation, drying then for to pouring the zirconium nitrate aqueous solution into according to first humidity method in the presence of the air in 500 ℃ of baked aluminum oxide, adds Co (NO again according to first humidity method
3)
26H
2The O aqueous solution floods the aqueous solution of Xiao Suangu once more after the drying, as above altogether repeatedly three times, cobalt contents meets the requirements in the complex catalyst precursor thing, adds binding agent, extrusion, pelletizing, drying, roasting, obtains qualified cobalt series catalyst after reduction is handled.
Fresh feed gas mixes the back after reacting under the listed processing condition of table 2 with circulation gas, the CO+H of about 45 volume %
2In first step reactor, transformed.The tail gas of A reactor takes off CO through antihypo
2After the processing, adopt methane autothermal oxidation device with the C1-C4 hydrocarbon conversion after, enter second stage reactor, under the listed processing condition of table 2, react.The quantity discharged of second stage Fischer-Tropsch synthesis tail gas is according to CO in the secondary circulation gas
2Determine with the content of rare gas element such as methane, guarantee CO+H in the circulation gas
2Content be higher than 75%.
The processing condition of table 2 Fischer-Tropsch synthesizer
| Processing condition | One-level | Secondary |
| Temperature of reaction, ℃ | 225 | 210 |
| Reaction pressure, MPa | 3.2 | 2.3 |
| Fresh feed gas and catalyzer ratio, Nm 3/m 3 | 1000 | 1000 |
| Recycled offgas and fresh feed airshed ratio, % | 3 | / |
Technical process of the present invention, the first step adopt Fe-series catalyst further to remove the catalyzer poison that contains in the unstripped gas when carrying out Fischer-Tropsch synthesis, and carry out water gas shift reaction, with H
2The ratio of/CO is increased to 2.0.Cobalt series catalyst is adopted in the second stage, overcomes the shortcoming of Fe-series catalyst, improves the carbon utilisation rate and the oil product yield of whole technology, and oily yield reaches 185 gram/m
3Synthetic gas significantly improves Fischer-Tropsch synthetic economic benefit.Because most synthetic gas transforms at second section quilt, given full play to the advantage of cobalt catalyst simultaneously, made the productive rate of kerosene and the above cut of diesel oil obviously improve, reached more than 78%.
Comparative Examples
Adopt the method disclosed in the CN1611565A to test, wherein, the two-stage Fischer-Tropsch is synthetic all to adopt paste state bed reactor, and all adopts iron catalyst in the described reactor.The circulation of one-level part tail gas, all the other remain discharge; One-level is discharged the fresh feed gas of tail gas as second order reaction, the most of circulation of secondary tail gas, and a small amount of discharger, one two inter-stages are not established and are taken off CO
2With hydrocarbon conversion devices such as methane.The concrete composition of one-level fresh feed gas sees Table 3.Main operational condition sees Table 4.Through test, resulting oily yield is 169 gram/m
3Synthetic gas.
The composition of table 3 unstripped gas
| Composition, v% | Ratio |
| CO | 39 |
| H 2 | 60 |
| CO 2 | 0.18 |
| Ar | 0.15 |
| CH 4 | 0.03 |
| N 2 | 0.63 |
The processing condition of table 4 Fischer-Tropsch synthesizer
| Processing condition | One-level | Secondary |
| Temperature of reaction, ℃ | 235 | 235 |
| Reaction pressure, MPa | 3.0 | 2.5 |
| Fresh feed gas and catalyzer ratio, Nm 3/m 3 | 5000 | / |
| Recycled offgas and fresh feed airshed ratio, % | 0.2 | 1 |
Embodiment 2
Present embodiment adopts technical process shown in Figure 1, after fresh feed gas is gasification, obtains H through purification and water-gas shift
2/ CO volume ratio is 1.3 synthetic gas, and concrete composition sees Table 5.
The composition of table 5 coal based synthetic gas raw material
| Composition, heavy % | Ratio |
| CO | 43.28 |
| H 2 | 56.29 |
| CO 2 | 0.07 |
| Ar | 0.05 |
| CH 4 | 0.08 |
| N 2 | 0.23 |
In the firsts and seconds reactor the iron system that adopts identical with cobalt series catalyst with embodiment 1.
Fresh feed gas and circulation gas are after 2 the mixed, to react about 75% CO+H under the listed processing condition of table 6 according to recycle ratio
2In first step reactor, transformed.The tail gas of A reactor takes off CO through antihypo
2After the processing, through methane autothermal oxidation device with the C1-C4 hydrocarbon conversion, tail gas after the processing enters second stage reactor, under the listed processing condition of table 6, react, most tail gas from second reactor loops back the A reactor inlet, a small amount of second reactor exhaust emissions, its quantity discharged is according to CO in the circulation gas
2Determine with the content of rare gas element such as methane, with CO+H in the circulation gas
2Content be higher than 75% and be as the criterion.
The processing condition of table 6 Fischer-Tropsch synthesizer
| Processing condition | One-level | Secondary |
| Temperature of reaction, ℃ | 250 | 215 |
| Cold high score pressure, MPa | 3.2 | 2.3 |
| Fresh feed gas and catalyzer ratio, Nm 3/m 3 | 1000 | / |
| Recycled offgas and fresh feed airshed ratio, % | 2 | / |
Because most synthetic gas is transformed in first step reactor, given full play to the advantage of iron catalyst, make olefins yield of the present invention be improved, particularly the yield of alkene reaches more than the 88v% in the C2-C4 product, very need to be fit to the factory of producing in high-yield olefin, simultaneously also produce more high-carbon alhpa olefin, can satisfy the demand of producing high value added products such as lubricating oil.
Claims (8)
1. Fischer-Tropsch synthesis method may further comprise the steps:
(1) makes the producing synthesis gas from coal raw material enter first step Fischer-Tropsch synthesis device, contact with ferrum-based catalyst, and under the Fischer-Tropsch synthesis condition, react;
(2) separate the first order reaction product, the remaining tail gas in reaction back removes CO
2After, enter C1-C4 hydrocarbon conversion device to produce CO and H
2, make the tail gas after the conversion enter second stage Fischer-Tropsch synthesis device then, contact with cobalt-base catalyst, and under the Fischer-Tropsch synthesis condition, react;
(3) separate the second order reaction product, discharge section tail gas, remaining tail gas return first step Fischer-Tropsch synthesis device and recycle.
2. according to the described Fischer-Tropsch synthesis method of claim 1, it is characterized in that described producing synthesis gas from coal is through purification and water-gas shift, and H
2/ CO volume ratio is 1.2-2.2.
3. according to the described Fischer-Tropsch synthesis method of claim 2, it is characterized in that the H of described producing synthesis gas from coal
2/ CO volume ratio is 1.4-1.8.
4. according to claim 1 or 3 described Fischer-Tropsch synthesis methods, it is characterized in that described first step Fischer-Tropsch synthesis device is the paste state bed reactor of one or more parallel connections, described second stage Fischer-Tropsch synthesis device is the fixed-bed reactor of one or more parallel connections.
5. according to the described Fischer-Tropsch synthesis method of claim 4, it is characterized in that the volume ratio of returning process tail gas that first step Fischer-Tropsch synthesis device recycles and fresh producing synthesis gas from coal raw material is 1-5.
6. according to the described Fischer-Tropsch synthesis method of claim 5, it is characterized in that the volume ratio of returning process tail gas that first step Fischer-Tropsch synthesis device recycles and fresh producing synthesis gas from coal raw material is 2-3.
7. according to claim 1 or 6 described Fischer-Tropsch synthesis methods, it is characterized in that, adopt hot salt of wormwood to take off CO
2Technology removes the CO in the described first step Fischer-Tropsch synthesis device tail gas
2Adopting natural gas auto-thermal oxidation process for preparing synthetic gas is CO and H with the described C1-C4 hydrocarbon conversion
2
8. according to the described Fischer-Tropsch synthesis method of claim 7, it is characterized in that the weight of described first step Fischer-Tropsch synthesis ferrum-based catalyst that device adopts consists of 100Fe: 5Cu: 5K
2O: 25SiO
2The weight of the cobalt-base catalyst that described second stage Fischer-Tropsch synthesis device is adopted consists of 15Co: 5Zr: 100Al
2O
3
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| KR100992835B1 (en) * | 2008-02-29 | 2010-11-08 | 한국화학연구원 | The continuous separation and discharge apparatus and method of solid catalysts and product product for Fischer-Tropsch synthesis reactions |
| JP5424566B2 (en) * | 2008-03-14 | 2014-02-26 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for producing synthesis gas in liquid hydrocarbon production process from natural gas |
| CN101863728B (en) * | 2009-04-17 | 2013-06-05 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
| CN101892063A (en) * | 2010-07-09 | 2010-11-24 | 神华集团有限责任公司 | Fischer-Tropsch synthesis method and system |
| CN103773410B (en) * | 2012-10-25 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of method improving liquid hydrocarbon yield |
| CN103965936B (en) * | 2013-02-06 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method of built-up type synthesizing liquid hydrocarbon |
| CN105983407B (en) * | 2015-01-29 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof for producing naphtha and drilling fluid |
| CN114806624A (en) * | 2021-01-27 | 2022-07-29 | 国家能源投资集团有限责任公司 | Method and system for preparing hydrocarbons from synthesis gas |
| CN113061071B (en) * | 2021-03-29 | 2024-02-13 | 上海睿碳能源科技有限公司 | Method and equipment for directly preparing olefin from synthesis gas based on slurry bed reactor |
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