CN1948438B - Two stage Fischer-Tropsch synthesis method - Google Patents
Two stage Fischer-Tropsch synthesis method Download PDFInfo
- Publication number
- CN1948438B CN1948438B CN2006101400204A CN200610140020A CN1948438B CN 1948438 B CN1948438 B CN 1948438B CN 2006101400204 A CN2006101400204 A CN 2006101400204A CN 200610140020 A CN200610140020 A CN 200610140020A CN 1948438 B CN1948438 B CN 1948438B
- Authority
- CN
- China
- Prior art keywords
- fischer
- tropsch synthesis
- gas
- tail gas
- section
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
This invention relates to a synthesis method of fischer-tropsch. Its preparation includes (a) Synthesis gas material enters into the first fischer-tropsch synthesis reactor to conduct fischer-tropsch synthesis reaction under the action of accelerant, (b) Segregating the first grade reaction product and letting parts of end gas return to the first fischer-tropsch reactor for recycling, and then letting C1-C4 alkanes containing in other surplus end gas to transform into synthetic gas.(c) Mixing the end gas transformed at step (b) and the second fischer-tropsch synthesis reaction circulation gas, and then entering the second fischer-tropsch synthesis reactor to conduct fischer-tropsch synthesis reaction under accelerant. (d) Segregating the second fischer-tropsch synthesis reaction product, and most of the gas returning to the second fischer-tropsch synthesis reactor for circulating reaction, and then evacuating other end gas. The transformation efficiency of CO+H2 is higher than 96% andthe yield of methyl hydride is lower than 3%, and the yield of unit space-time of accelerant reaches 185 g/kg*h.
Description
Technical field
The present invention relates to a kind of is the Fischer-Tropsch synthesis method of raw material production hydro carbons with the synthetic gas, relates in particular to a kind of two stage Fischer-Tropsch synthesis method.
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, by coal, Sweet natural gas or other material production synthetic gas, again according to the requirement of fischer-tropsch synthetic catalyst to synthetic gas, by water-gas shift and purified synthesis gas technology synthetic gas is handled, to handle the back synthetic gas is that raw material is by the synthetic hydro carbons of producing of Fischer-Tropsch, while by-product oxygenatedchemicals, adopt sophisticated Petroleum Processing Technology to process then, produce high-quality eco-friendly oil product, its core is the Fischer-Tropsch synthetic technology.As seen develop new Fischer-Tropsch synthesis process, have very important significance developing alternative oil manufacture technology.
" coal liquefaction " introduced the sophisticated Fischer-Tropsch synthesis process of Sasol company, its technical process is single hop technology substantially, the slurry attitude bed process that the Arge technology that adopts fixed bed, the Kellogg technology that the employing fluidized-bed is arranged and employing slurry attitude bed are arranged according to the difference of type of reactor, the tail gas of Arge technology is as the raw material of Kellogg technology in Sasol I factory, and not seeing has the two-part technical process of adopting same reactor.
Patent CN 200310108146.X 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.Be not provided with in the middle of this technology and take off CO
2With the step of the hydrocarbon conversions such as methane, oily yield can only reach 180 gram/m
3Synthetic gas.
Summary of the invention
The object of the present invention is to provide a kind of two stage Fischer-Tropsch synthesis method, overcome with the synthetic gas methane production height that exists when to be raw material by conventional Fischer-Tropsch synthesis method produce liquid product, the shortcoming that the CO utilization ratio is low, improve the space-time yield of catalyzer simultaneously.
Two stage Fischer-Tropsch synthesis method provided by the invention may further comprise the steps:
A) make raw material of synthetic gas enter first section Fischer-Tropsch synthesis device, under the effect of catalyzer, carry out Fischer-Tropsch synthesis;
B) separate first section Fischer-Tropsch synthesis product, part tail gas returns first section Fischer-Tropsch synthesis device circulating reaction, is synthetic gas with the C1～C4 hydrocarbon conversion that contains in all the other tail gas then;
C) will mix from the recycled offgas of the tail gas after the conversion of step b), enter second section Fischer-Tropsch synthesis device, under the effect of catalyzer, carry out Fischer-Tropsch synthesis with second section Fischer-Tropsch synthesis;
D) separate second section Fischer-Tropsch synthesis product, most of tail gas returns second section Fischer-Tropsch synthesis device circulating reaction, discharges remaining tail gas.
Further describe two stage Fischer-Tropsch synthesis method of the present invention below, but therefore the present invention is not subjected to any restriction.
Step b) described in the above-mentioned Fischer-Tropsch synthesis method can for: separate first section Fischer-Tropsch synthesis product, part tail gas returns first section Fischer-Tropsch synthesis device circulating reaction, and remaining tail gas is removed CO
2, CO in tail gas
2Content be 1 volume %-20 volume %, will remove CO then
2After tail gas in C1～C4 hydrocarbon conversion of containing be synthetic gas.Remove the CO in the tail gas
2Method can adopt the CO that removes commonly used
2Processing method, for example, hot salt of wormwood takes off CO
2Method or WATER-WASHING METHOD.Hot salt of wormwood takes off CO
2Method device commonly used is that hot salt of wormwood takes off CO
2Adsorption tower, the saleratus of generation removes CO at regenerator column
2, the solution of potassium carbonate that obtains returns adsorption tower again.WATER-WASHING METHOD only need be established water washing tank and be got final product.
Synthetic gas in the step a) can be produced by coal, Sweet natural gas or organism, but must remove the material to the toxic effect of fischer-tropsch synthetic catalyst such as its contained sulphur through purifying." gelatin liquefaction technology " (Chemical Industry Press, author: Gao Jinsheng, Zhang Dexiang, publication time: in March, 2005) described the correlation technique for preparing synthetic gas, purified synthesis gas and conversion in detail.H in the synthetic gas
2With the volume ratio of CO be 0.67～2.2, be preferably 1.0～1.8.
First section Fischer-Tropsch synthesis carries out under following reactant condition in the step a): temperature of reaction is 200～280 ℃, is preferably 225～260 ℃; Reaction pressure is 15～50bar, is preferably 20～40bar; The volume ratio of recycled offgas and fresh synthesis gas raw material is 1～7, is preferably 1～3; The volume ratio of fresh synthesis gas raw material and catalyzer is 200～5000, is preferably 500～3000.Fischer-tropsch reaction of the present invention belongs to the low temperature Fischer-Tropsch synthesis.
In the step b), the tail gas of 20-80 volume % returns first section Fischer-Tropsch synthesis device circulating reaction.With the C1～C4 hydrocarbon conversion that contains in all the other tail gas is the processing method that the method for synthetic gas can adopt known Sweet natural gas preparing synthetic gas, and for example natural gas auto-thermal oxidation preparing synthetic gas method is CO and H with the described C1-C4 hydrocarbon conversion
2
In the step c), the recycled offgas of second section Fischer-Tropsch synthesis be 1～5 from the tail gas after the conversion of step b) with volume ratio, be preferably 2～3 and mix, enter second section Fischer-Tropsch synthesis device, the quantity discharged of tail gas is looked CO+H in the circulation gas
2Content and decide, guarantee CO+H
2Content be not less than 60%; Second section Fischer-Tropsch synthesis carries out under following reaction conditions: temperature of reaction is 190～270 ℃, is preferably 200～250 ℃; Reaction pressure is 15～50bar, is preferably 15～35bar; Volume ratio from tail gas after the conversion of step b) and catalyzer is 200～2000, is preferably 500～1500.
Improve the severity of first section Fischer-Tropsch synthesis process condition, the per pass conversion that makes the synthetic CO of the section of winning Fischer-Tropsch is between 65%～85%, guarantee the space-time yield of catalyzer, reduce the severity of the second Fischer-Tropsch synthesis process condition, make the per pass conversion of the synthetic CO of second section Fischer-Tropsch be lower than 35%, the productive rate of methane that guarantees whole technology is low, oil product yield height.
Step a) and c) in the Fischer-Tropsch synthesis device adopt paste state bed reactor.First section Fischer-Tropsch synthetic reactor can be one or more paste state bed reactors, only establishes a paste state bed reactor for second section.
Employed catalyzer can be iron system or cobalt system slurry attitude bed catalyst in step a) and the step c).For example, employed catalyzer can consist of 100Fe:5Cu:5K for weight in the step a)
2O:25SiO
2Fe-series catalyst or weight consist of 15Co:5Zr:100Al
2O
3Cobalt series catalyst; Step C) employed catalyzer can consist of 100Fe:5Cu:5K for weight in
2O:25SiO
2Fe-series catalyst or weight consist of 15Co:5Zr:100Al
2O
3Cobalt series catalyst.Process natural gas base synthetic gas adopts cobalt series catalyst, and the processing coal based synthetic gas adopts Fe-series catalyst, and what need particularly point out is: because the water-gas shift activity of cobalt series catalyst is very low, and CO in the product
2Ratio very low, adopt the technology of cobalt series catalyst, need not establish one or the two intersegmental CO that take off
2Step.
In the step d), the tail gas of 20-95 volume % returns second section Fischer-Tropsch synthesis device circulating reaction, discharges remaining tail gas.
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, especially with petroleum naphtha, diesel oil distillate and wax primary product.
The wax of producing in the Fischer-Tropsch synthesis device passes through to discharge as product after interior strainer that is provided with of reactor 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 high low-temperature separator, the temperature of its low-temperature separator can not be higher than 50 ℃, service temperature is low more good more, minimumly can not be lower than 5 ℃, and preferred temperature is 10 ℃.
Compared with prior art, two stage Fischer-Tropsch synthesis method provided by the present invention has following beneficial effect:
Take off CO by between two sections Fischer-Tropsch are synthetic, being provided with
2With the step of the hydrocarbon conversion, improve the reaction atmosphere in second section Fischer-Tropsch synthesis device, improve CO+H
2Dividing potential drop, reduce the outer discharge capacity of tail gas, thereby improve CO+H
2Transformation efficiency.While CO
2But competitive adsorption influences the Fischer-Tropsch composite reactive of catalyzer on the surface of catalyzer, remove CO
2Can improve second section activity of such catalysts.Hydrocarbon gass such as methane are converted into CO+H
2, can improve oil product yield of the present invention effectively, reduce the productive rate of methane.The inventive method is produced and is obtained petroleum naphtha, diesel oil and wax, the rich simultaneously oxygenatedchemicals that produces.
The present invention is by rationally regulating and control the severity of two-stage process parameter, the processing parameter of controlling first section is comparatively harsh, can improve the transformation efficiency of CO, thereby improve the unit space-time yield of catalyzer, second section processing parameter comparatively relaxes, reduce the productive rate of methane, realize that whole technology has the purpose of greater catalytic agent space-time yield, low methane production.
The CO+H of the inventive method
2Transformation efficiency be higher than 96%, the productive rate of methane is lower than 3%, the unit space-time yield of catalyzer reaches 185 gram oil product/kg catalyzer hour.
Description of drawings
Fig. 1 is the schema of two stage Fischer-Tropsch synthesis technique 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 equipment of many necessity when having omitted industrial application among the figure is as process furnace, pump, valve and interchanger etc.
As shown in Figure 1, through purifying and adjust CO and H
2Volume ratio be that 0.67～2.2 fresh synthesis gas raw material 1 is mixed into unstripped gas 2 with recycled offgas 12, unstripped gas 2 through interchanger 105 and 103 and the Fischer-Tropsch synthetic heat exchange after, enter first section Fischer-Tropsch synthesis device 102, Fischer-Tropsch synthesis takes place under the effect of fischer-tropsch synthetic catalyst, because Fischer-Tropsch synthesis is a strong exothermal reaction, adopt steam coils that reaction heat is taken out, the temperature of whole reactor is by the pressure-controlling of steam pockets 101, by-product water vapor 26, the wax that generates is by built-in strainer and the catalyst separating of reactor, obtain product wax 13, the mixture 3 of the lighting end of reacted unstripped gas and part Fischer-Tropsch synthetic comes out from the top of reactor 102, after interchanger 103 heat exchange, carry out gas-liquid separation with unstripped gas at hot high score 104, 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 ℃, carry out gas-liquid separation at cold high score 106, isolate cold high score product 6 and tail gas 5, the tail gas 5 of discharging from cold high score top is divided into two portions, a part 12 is mixed Returning reactor with fresh feed gas 1 after recycle compressor 107 superchargings, remaining tail gas 7 is through taking off CO
2Device 108 removes CO
2After 18, after being synthetic gas with C1～C4 hydrocarbon conversion, mixes in hydrocarbon conversion device 109 with second section recycled offgas 35, after second section recycle compressor 119 supercharging, gas mixture 40 is after second section interchanger 115 and 113 and second sections Fischer-Tropsch process exhaust heat exchange, enter second section Fischer-Tropsch synthesis device 112 and carry out the synthetic conversion of Fischer-Tropsch, the same with first section Fischer-Tropsch synthesis device, the temperature of reaction of second section Fischer-Tropsch synthesis device is by steam pockets 111 controls, by-product water vapor 25, second section synthetic wax that generates of Fischer-Tropsch is through reactor built-in strainer and catalyst separating, obtain Fischer-Tropsch synthetic wax 43, its with obtain 88 after first section Fischer-Tropsch synthetic wax 13 mixes and go out device as product, second section Fischer-Tropsch synthesis device overhead stream 33 carries out gas-liquid separation at hot high score 114 after interchanger 113 and unstripped gas heat exchange, isolate hot high score product 37 and hot high score gas 34, hot high score gas 34 again with the unstripped gas heat exchange after, fall within the range of about 50 ℃, carry out gas-liquid separation at cold high score 116, isolate cold high score product 36 and cold high score gas 35, the quantity discharged of tail gas 38 is by CO+H in the tail gas
2Content decision, to guarantee CO+H in the tail gas
2Content be not less than 75%, CO+H in tail gas
2Content be higher than 75%, reduce quantity discharged; CO+H in tail gas
2Content be lower than 75%, then increase quantity discharged.Remaining tail gas with handle after first section tail gas 10 mixes and returns second section Fischer-Tropsch synthesis device and enter the mouth; After one or two sections cold high score product 6 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 one or two sections hot high score products 37 and 40 mix 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 35 that divides of heat mixes with cold high score product after cooling to 5～50 ℃.
Embodiment 1
Present embodiment adopts technical process shown in Figure 1, after fresh feed gas is gasification, through the H that purifies and water-gas shift obtains
2With the volume ratio of CO be 1.6 synthetic gas, concrete composition sees Table 1.
The composition of table 1 fresh synthesis gas
| Composition | Ratio (volume %) |
| CO | 38.11 |
| H 2 | 61.11 |
| CO 2 | 0.12 |
| Ar | 0.13 |
| CH 4 | 0.08 |
| N 2 | 0.45 |
Present embodiment all adopts Fe-series catalyst for two sections, and the weight of catalyzer consists of 100Fe:5Cu:5K
2O:25SiO
2The 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 NaCO
3Solution precipitates, and filters then and wash not conform to alkali; With the filter cake making beating, add quantitative K
2SiO
3, and add HNO
3Unnecessary potassium ion is washed off, washing and filtering again, again with the spray-dried size range that obtains in filter cake making beating back at 60～90 microns granules of catalyst, after reduction, can be used as qualified Fe-series catalyst and use.
Fresh feed gas mixes the back and react 75% CO+H under the listed processing condition of table 2 with circulation gas
2Transformed.70% tail gas by after the recycle compressor supercharging with fresh feed gas mixings Returning reactor, remaining 30% tail gas passes through water elution CO
2After the processing, with CO
2Concentration reduce to 20%, enter C1-C4 hydrocarbon catalyticing oxidation device, will be CO+H based on the hydrocarbon conversion of methane
2, mix with second section tail gas then, after second section recycle compressor supercharging, enter second section Fischer-Tropsch synthesis device, under the listed processing condition of table 2, to react, the quantity discharged of second section Fischer-Tropsch synthesis tail gas is according to CO in second section circulation gas
2Determine with the content of rare gas element such as methane, guarantee CO+H in the circulation gas
2Content be higher than 70%.
The processing condition of table 2 Fischer-Tropsch synthesizer
| Processing condition | First section | Second section |
| Temperature of reaction, ℃ | 235 | 220 |
| Reaction pressure, MPa | 2.5 | 2.5 |
| Fresh feed gas and catalyzer ratio, Nm 3/m 3 | 1000 | 600 |
| Recycled offgas and raw material of synthetic gas throughput ratio, % | 3 | 4 |
Adopt this technical process, first section turns round under comparatively harsh processing condition, improves the spatiotemporal efficiency of catalyzer, and second section is comparatively turning round under the demulcent processing condition, reduces methane and CO
2Deng productive rate, improve the yield of the oil product of whole technology, make the productive rate of whole technology methane be lower than 3%, the oil product space-time yield of catalyzer is 185g oil product/kg catalyzer hour, CO+H
2Transformation efficiency greater than 96%.
Embodiment 2
Present embodiment adopts technical process shown in Figure 1, takes off CO but removed
2Device 108.After fresh feed gas is natural gas gasifying, the H that after purifying, obtains
2With the volume ratio of CO be 2 synthetic gas, concrete composition sees Table 3.
The composition of table 3 fresh synthesis gas
| Composition | Ratio (volume %) |
| CO | 33.14 |
| H 2 | 66.29 |
| CO 2 | 0.04 |
| Ar | 0.10 |
| CH 4 | 0.05 |
| N 2 | 0.38 |
Present embodiment all adopts cobalt series catalyst for two sections, and the weight of cobalt catalyst consists of 15Co:5Zr:100Al
2O
3The preparation method uses rotary drum dehydration by evaporation, drying then for earlier pouring the zirconium nitrate aqueous solution into according to first wetting method in 500 ℃ of baked aluminum oxide in air in advance, 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 a certain amount of binding agent, through moulding, drying, roasting, and reduction obtains qualified cobalt series catalyst after handling.
Fresh feed gas mixes the back and react 78% CO+H under the listed processing condition of table 4 with circulation gas
2Transformed.70% tail gas by after the recycle compressor supercharging with the mixed of fresh feed gas with 2: 1, Returning reactor, remaining 3 0% tail gas will be CO+H based on the hydrocarbon conversion of methane after handling through methane autothermal oxidation device
2, mix with second section tail gas then, after second section recycle compressor supercharging, enter second section Fischer-Tropsch synthesis device, under the listed processing condition of table 4, to react, the quantity discharged of second section Fischer-Tropsch synthesis tail gas is according to CO in second section 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 4 Fischer-Tropsch synthesizer
| Processing condition | First section | Second section |
| Temperature of reaction, ℃ | 215 | 205 |
| Reaction pressure, MPa | 2.5 | 2.5 |
| Fresh feed gas and catalyzer ratio, Nm 3/m 3 | 1000 | 600 |
| Recycled offgas and fresh feed airshed ratio, % | 2 | 3 |
Adopt this technical process, one section turns round under comparatively harsh processing condition, improves the spatiotemporal efficiency of catalyzer, and two sections are comparatively turning round under the demulcent processing condition, reduce methane and CO
2Deng productive rate, improve the yield of the oil product of whole technology, make the productive rate of whole technology methane be lower than 3%, the oil product space-time yield of catalyzer is 188g oil product/kg catalyzer hour, CO+H
2Transformation efficiency greater than 96%.
Claims (9)
1. one kind is the Fischer-Tropsch synthesis method of raw material production hydrocarbon with the synthetic gas, may further comprise the steps:
A) make raw material of synthetic gas enter first section Fischer-Tropsch synthesis device, under the effect of catalyzer, carry out Fischer-Tropsch synthesis, temperature of reaction is 200～280 ℃, reaction pressure is 15～50bar, the volume ratio of recycled offgas and fresh synthesis gas raw material is 1～7, and the volume ratio of fresh synthesis gas raw material and catalyzer is 200～5000;
B) separate first section Fischer-Tropsch synthesis product, part tail gas returns first section Fischer-Tropsch synthesis device circulating reaction, then C1～C4 the hydrocarbon that contains in all the other tail gas is converted into synthetic gas;
C) will mix from the recycled offgas of the tail gas after the conversion of step b) with second section Fischer-Tropsch synthesis, enter second section Fischer-Tropsch synthesis device, under the effect of catalyzer, carry out Fischer-Tropsch synthesis, temperature of reaction is 190～270 ℃, reaction pressure is 15～50bar, the recycled offgas of described second section Fischer-Tropsch synthesis be 1～5 from the volume ratio of the tail gas after the conversion of step b), be 200～2000 from the volume ratio of tail gas after the conversion of step b) and catalyzer;
D) separate second section Fischer-Tropsch synthesis product, most of tail gas returns second section Fischer-Tropsch synthesis device circulating reaction, discharges remaining tail gas.
2. Fischer-Tropsch synthesis method according to claim 1 is characterized in that, step b) is for separating first section Fischer-Tropsch synthesis product, and part tail gas returns first section Fischer-Tropsch synthesis device circulating reaction, and remaining tail gas is removed CO
2, CO in tail gas
2Content be 1 volume %-20 volume %, will remove CO then
2After tail gas in C1～C4 hydrocarbon of containing be converted into synthetic gas.
3. Fischer-Tropsch synthesis method according to claim 2 is characterized in that, adopts hot salt of wormwood to take off CO in the step b)
2Method or WATER-WASHING METHOD remove the CO in the described tail gas
2Adopt natural gas auto-thermal oxidation preparing synthetic gas method that described C1-C4 hydrocarbon is converted into CO and H
2
4. Fischer-Tropsch synthesis method according to claim 3, it is characterized in that, first section Fischer-Tropsch synthesis carries out under following reaction conditions in the step a): temperature of reaction is 225～260 ℃, reaction pressure is 20～40bar, the volume ratio of recycled offgas and fresh synthesis gas raw material is 1～3, and the volume ratio of fresh synthesis gas raw material and catalyzer is 500～3000; In the step c), second section Fischer-Tropsch synthesis carries out under following reaction conditions: temperature of reaction is 200～250 ℃, reaction pressure is 15～35bar, the recycled offgas of second section Fischer-Tropsch synthesis be 2～3 from the volume ratio of the tail gas after the conversion of step b), be 500～1500 from the volume ratio of tail gas after the conversion of step b) and catalyzer.
5. Fischer-Tropsch synthesis method according to claim 4 is characterized in that, synthetic gas described in the step a) is through purification and water-gas shift, and H
2With the volume ratio of CO be 0.67～2.2.
6. according to each the described Fischer-Tropsch synthesis method among the claim 1-5, it is characterized in that described first section Fischer-Tropsch synthesis device is one or more paste state bed reactors, described second section Fischer-Tropsch synthesis device is a paste state bed reactor.
7. according to the described Fischer-Tropsch synthesis method of claim 6, it is characterized in that in the step b), the tail gas of 20-80 volume % returns first section Fischer-Tropsch synthesis device circulating reaction; In the step d), the tail gas of 20-95 volume % returns second section Fischer-Tropsch synthesis device circulating reaction.
8. according to the described Fischer-Tropsch synthesis method of claim 7, it is characterized in that step a) and c) in employed catalyzer determine that by the source of synthetic gas producing synthesis gas from coal adopts Fe-series catalyst, the Sweet natural gas preparing synthetic gas adopts cobalt series catalyst.
9. Fischer-Tropsch synthesis method according to claim 8 is characterized in that, employed catalyzer is that weight consists of 100Fe:5Cu:5K in the step a)
2O:25SiO
2Fe-series catalyst or weight consist of 15Co:5Zr:100Al
2O
3Cobalt series catalyst; Employed catalyzer is that weight consists of 100Fe:5Cu:5K in the step c)
2O:25SiO
2Fe-series catalyst or weight consist of 15Co:5Zr:100Al
2O
3Cobalt series catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101400204A CN1948438B (en) | 2006-10-08 | 2006-10-08 | Two stage Fischer-Tropsch synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101400204A CN1948438B (en) | 2006-10-08 | 2006-10-08 | Two stage Fischer-Tropsch synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1948438A CN1948438A (en) | 2007-04-18 |
| CN1948438B true CN1948438B (en) | 2010-06-30 |
Family
ID=38018064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101400204A Active CN1948438B (en) | 2006-10-08 | 2006-10-08 | Two stage Fischer-Tropsch synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1948438B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892063A (en) * | 2010-07-09 | 2010-11-24 | 神华集团有限责任公司 | Fischer-Tropsch synthesis method and system |
| CN103396826B (en) * | 2013-08-14 | 2015-06-10 | 神华集团有限责任公司 | Two-stage series-connected Fischer-Tropsch synthesis system and process thereof |
| CN106221720B (en) * | 2016-08-19 | 2018-03-13 | 武汉凯迪工程技术研究总院有限公司 | Selective catalytic oxidation converts the comprehensive utilization process of Fischer-Tropsch process exhaust |
| CN112625727A (en) * | 2020-11-29 | 2021-04-09 | 上海兖矿能源科技研发有限公司 | Series system for Fischer-Tropsch synthesis |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304913A (en) * | 2000-07-17 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Process for synthesizing hydrocarbon from syntehtic gas |
| US20010047040A1 (en) * | 1999-03-30 | 2001-11-29 | Syntroleum Corporation, Delaware Corporation | System and method for converting light hydrocarbons into heavier hydrocarbons with a plurality of synthesis gas subsystems |
| WO2003018519A1 (en) * | 2001-08-23 | 2003-03-06 | Chevron U.S.A. Inc. | Process for converting synthesis gas into hydrocarbonaceaous products |
| WO2005019384A1 (en) * | 2003-08-22 | 2005-03-03 | Sasol Technology (Proprietary) Limited | Process for synthesising hydrocarbons |
-
2006
- 2006-10-08 CN CN2006101400204A patent/CN1948438B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010047040A1 (en) * | 1999-03-30 | 2001-11-29 | Syntroleum Corporation, Delaware Corporation | System and method for converting light hydrocarbons into heavier hydrocarbons with a plurality of synthesis gas subsystems |
| CN1304913A (en) * | 2000-07-17 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Process for synthesizing hydrocarbon from syntehtic gas |
| WO2003018519A1 (en) * | 2001-08-23 | 2003-03-06 | Chevron U.S.A. Inc. | Process for converting synthesis gas into hydrocarbonaceaous products |
| WO2005019384A1 (en) * | 2003-08-22 | 2005-03-03 | Sasol Technology (Proprietary) Limited | Process for synthesising hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1948438A (en) | 2007-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101955788B (en) | Fischer-Tropsch synthesis method and system | |
| CN100575457C (en) | A kind of Fischer-Tropsch synthesis method | |
| CN105944751B (en) | A kind of catalyst directly preparing aromatic compound for synthesis gas and its preparation and application | |
| CN103664447B (en) | The method of synthesis gas alkene processed | |
| CN111117702B (en) | Hydrocracking method for increasing yield of heavy naphtha and jet fuel fraction | |
| CN101544539B (en) | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate | |
| CN101270297B (en) | Technique for synthesis of gas cobalt base Fischer-Tropsch synthetic liquid fuel and byproduct of aromatic hydrocarbons with coal base | |
| CN102585950B (en) | Method for preparing synthetic natural gas by coke oven gas in combination with straw gas | |
| CN101928194B (en) | Tropsch synthesis method of fixed bed | |
| CN1948438B (en) | Two stage Fischer-Tropsch synthesis method | |
| CN101016494A (en) | Method of producing liquefied petroleum gas | |
| CN104098419B (en) | Coal, natural gas combination preparing light olefins from methanol system and method | |
| CN104220159B (en) | For the catalysis active body from synthesis gas synthesis dimethyl ether | |
| CN1167650C (en) | Process for synthesizing hydrocarbon from syntehtic gas | |
| CN103396826B (en) | Two-stage series-connected Fischer-Tropsch synthesis system and process thereof | |
| CN102041019B (en) | Method for coproducing substitute natural gas through coal liquefaction | |
| CN107486226B (en) | Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas | |
| CN101928598B (en) | Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion | |
| CN102746870A (en) | FT synthesis technology | |
| CN102464299A (en) | Method for producing hydrogen through fluidized-bed methane steam reforming | |
| CN101979475A (en) | Process for synthesizing natural gas by performing methanation on coke oven gas | |
| CN101811698A (en) | Method for producing carbon disulfide | |
| CN103183319A (en) | Method, device and reaction system for hydrocarbon preparation by light hydrocarbon steam reforming | |
| CN210560263U (en) | Device for preparing Fischer-Tropsch wax by utilizing coke oven gas | |
| CN103183318A (en) | Method for hydrogen production by light hydrocarbon steam reforming in moving bed and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |