CN112625727A - Series system for Fischer-Tropsch synthesis - Google Patents
Series system for Fischer-Tropsch synthesis Download PDFInfo
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- CN112625727A CN112625727A CN202011366003.9A CN202011366003A CN112625727A CN 112625727 A CN112625727 A CN 112625727A CN 202011366003 A CN202011366003 A CN 202011366003A CN 112625727 A CN112625727 A CN 112625727A
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- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000011817 metal compound particle Substances 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
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- 239000001993 wax Substances 0.000 description 16
- 238000000926 separation method Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
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- 229910052742 iron Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- 230000009471 action Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 230000008901 benefit Effects 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 239000003502 gasoline Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a series system for Fischer-Tropsch synthesis, which comprises a first-stage Fischer-Tropsch synthesis system and a second-stage Fischer-Tropsch synthesis system, wherein the first-stage Fischer-Tropsch synthesis system and the second-stage Fischer-Tropsch synthesis system are connected in series, tail gas of the first-stage Fischer-Tropsch synthesis system enters the second-stage Fischer-Tropsch synthesis system for reaction, a reactor of the first-stage Fischer-Tropsch synthesis system is filled with a protective catalyst, and a reactor of the second-stage Fischer-Tropsch synthesis system is filled with a synthetic catalyst. Compared with the prior art, the invention reduces the energy consumption and material consumption generated in the desulfurization process, reduces the consumption of the catalyst per ton product, and reduces the construction and operation costs of the Fischer-Tropsch synthesis device.
Description
Technical Field
The invention relates to a Fischer-Tropsch synthesis technology, in particular to a series system for Fischer-Tropsch synthesis.
Background
Fischer-tropsch synthesis is a catalytic reaction in which carbon monoxide and hydrogen are converted to hydrocarbons and oxygenated organics using a group VIII metal (e.g., iron, cobalt, ruthenium) catalyst. At present, typical foreign Fischer-Tropsch synthesis processes comprise the Arge, SSPD, Synthon and SAS processes of Sasol, the SMDS process of Shell, the AGC-21 process of Exxon and the like, and domestic Shanghai Yan mining energy technology research and development Limited company, Chinese synthetic oil technology Limited company, Shenhua coal oil-making chemical industry Limited company and the like also have respective researched Fischer-Tropsch synthesis technologies and realize industrialization. Shanghai Yan mine energy science and technology research and development company is the only company which has low-temperature Fischer-Tropsch synthesis technology and high-temperature Fischer-Tropsch synthesis technology and realizes industrialization at present in China.
CN200310108146.X discloses a process for producing liquid fuel from synthesis gas, the Fischer-Tropsch synthesis unit of the process is divided into two stages, the products are paraffin and condensate, the raw gas of the second stage Fischer-Tropsch synthesis is tail gas of the first stage Fischer-Tropsch synthesis, part of the tail gas of the two synthesis units is circulated, the second stage Fischer-Tropsch tail gas is deeply cooled to remove most of components above C3 in the tail gas, and the components and the paraffin and the condensate generated by the two stage Fischer-Tropsch synthesis units enter an oil refining unit together to produce the liquid fuel.
CN200610140019.1 discloses a Fischer-Tropsch synthesis method and a system, and the method comprises the following steps: a) to contain CO and H2The raw material gas enters a first section of Fischer-Tropsch synthesis reactor to carry out Fischer-Tropsch synthesis reaction, and a first section of Fischer-Tropsch synthesis reaction product is obtained; b) separating the product of the first-stage Fischer-Tropsch synthesis reaction to separate water from the unconverted tail gas to obtain a hydrocarbon product and the unconverted tail gas of the first-stage Fischer-Tropsch synthesis reaction; c) feeding the unconverted tail gas obtained in the step b) into a second section of Fischer-Tropsch synthesis reactor to carry out Fischer-Tropsch synthesis reaction so as to obtain a second section of Fischer-Tropsch synthesis reaction product; d) separating the second section of Fischer-Tropsch synthesis reaction product to separate water from the unconverted tail gas to obtain a hydrocarbon product and the unconverted tail gas of the second section of Fischer-Tropsch synthesis reaction, wherein one part of the unconverted tail gas of the second section of Fischer-Tropsch synthesis reaction returns to the second section of Fischer-Tropsch synthesis reactor for circular reaction.
CN200610140019.1 discloses a Fischer-Tropsch synthesis method, which comprises the following steps: (1) the synthesis gas raw material prepared from coal enters the first-stage Fischer-Tropsch synthesisA reactor which contacts and reacts with the iron-based catalyst; (2) separating the first-stage reaction product, and removing CO from the residual tail gas after the reaction2Then, enter C1－C4Hydrocarbon conversion plant to produce CO and H2Then, the converted tail gas enters a second-stage Fischer-Tropsch synthesis reactor, and contacts and reacts with a cobalt-based catalyst; (3) separating the second-stage reaction product, discharging partial tail gas, and returning the rest tail gas to the first-stage Fischer-Tropsch synthesis reactor for recycling.
CN201310353571.9 discloses a two-stage series Fischer-Tropsch synthesis system and a process thereof, wherein the system comprises: at least one first-stage high-temperature Fischer-Tropsch synthesis slurry bed reactor, wherein the synthesis gas is subjected to a high-temperature Fischer-Tropsch synthesis reaction in the reactor to mainly generate gasoline and low-carbon olefin; at least one low-carbon olefin separator for separating the low-carbon olefins generated in the first stage reactor; and at least one second-stage low-temperature Fischer-Tropsch synthesis slurry bed or fixed bed reactor, wherein the tail gas of the synthesis gas from the first-stage reactor is directly subjected to low-temperature Fischer-Tropsch synthesis reaction in the second-stage reactor without any component adjustment or transformation to mainly generate diesel oil and Fischer-Tropsch wax, and the Fischer-Tropsch wax or paraffin wax is supplemented or circulated into the first-stage high-temperature slurry bed reactor to maintain the stable liquid level in a gas-solid-liquid reaction system in the first-stage high-temperature slurry bed reactor.
The first-stage reactor and the second-stage reactor of the existing Fischer-Tropsch synthesis series technology are both filled with reduced Fischer-Tropsch synthesis catalysts. The Fischer-Tropsch synthesis catalyst, especially the cobalt-based catalyst, has high requirements on the sulfur content in the synthesis gas, and in order to prevent the sulfur poisoning of the catalyst, a desulfurization device or even a fine desulfurization device is generally required to be arranged in the synthesis gas preparation process at the upstream of the Fischer-Tropsch synthesis system, so that a large amount of material consumption and energy consumption are generated.
In addition, since the fischer-tropsch catalyst is gradually deactivated during use, the prior art requires periodic replacement of the catalyst in the reactor with fresh catalyst in order to ensure a high conversion. The catalyst replaced in the reactor, i.e. the spent catalyst, although still having a relatively high reactivity (more than 70% of the fresh catalyst), can nevertheless result in a too low efficiency to cost ratio (benefit/operating cost ratio) and poor economics if it is used continuously for the production of fischer-tropsch synthesis products. It is now common practice to subject spent catalysts to oxidation treatment and then to landfill treatment as solid waste or to recycle as scrap metal.
Disclosure of Invention
The present invention aims to overcome the defects of the prior art and provide a series system for Fischer-Tropsch synthesis, which can reduce the consumption of catalyst per ton of product and the energy and material consumption generated in the desulfurization process.
The purpose of the invention can be realized by the following technical scheme: the utility model provides a series system for ft synthesis, includes one-level ft synthesis system and second grade ft synthesis system, its characterized in that, one-level ft synthesis system and second grade ft synthesis system series connection, wherein the tail gas of one-level ft synthesis system gets into the reaction of second grade ft synthesis system, the reactor of one-level ft synthesis system in pack the protection catalyst, the reactor of second grade ft synthesis system in pack the synthetic catalyst.
Sending the synthetic gas into a first-stage Fischer-Tropsch synthesis system, wherein the synthetic gas undergoes Fischer-Tropsch synthesis reaction and sulfur adsorption reaction in a reactor filled with a protective catalyst, and H in the synthetic gas2And partially converting CO into a Fischer-Tropsch synthesis product under the action of the protective catalyst, and reacting sulfur on the surface of the protective catalyst to generate solid-phase sulfide. And condensing and separating the product at the outlet of the reactor to obtain tail gas, conveying the tail gas to a second-stage Fischer-Tropsch synthesis system, and converting the tail gas into a Fischer-Tropsch synthesis product under the action of a synthesis catalyst.
The protective catalyst is one or more of the following combinations: the catalyst comprises a Fischer-Tropsch synthesis waste catalyst, a reduced Fischer-Tropsch synthesis catalyst, a partially reduced Fischer-Tropsch synthesis catalyst, an oxidized Fischer-Tropsch synthesis catalyst and a desulfurizing agent. Spent fischer-tropsch synthesis catalyst is catalyst that is removed from the reactor in order to maintain the activity of the catalyst in the bed at a high level. Despite its reduced activity, the catalyst surface still has a high proportion of reactive sites, which can either convert the synthesis gas into a Fischer-Tropsch synthesis product or react with free sulfur to form solid metal sulfides. The protective catalyst can improve the desulfurization rate by increasing the proportion of the oxidized Fischer-Tropsch synthesis catalyst and the desulfurizing agent on the basis of completely utilizing the Fischer-Tropsch synthesis catalyst, and can also improve the conversion rate of the Fischer-Tropsch synthesis by increasing the proportion of the reduced Fischer-Tropsch synthesis catalyst and the partially reduced Fischer-Tropsch synthesis catalyst.
The Fischer-Tropsch synthesis waste catalyst is a catalyst which is replaced out of the reactor in the running process of a two-stage Fischer-Tropsch synthesis system or other Fischer-Tropsch synthesis systems. The Fischer-Tropsch synthesis catalyst mainly comprises transition metals (iron, cobalt, Liaoning, etc.) or compounds (oxides, carbides, etc.) thereof, and can catalyze H under the conditions of high temperature and high pressure2And CO conversion to hydrocarbons, oxygenated organics, CO2Water, etc. and these components may react with the gaseous sulfide in the synthesis gas to produce solid metal sulfide. The desulfurizing agent is metal or metal compound particles which can react with gas sulfide to generate solid sulfide, such as iron powder, iron oxide particles, zinc oxide particles and the like.
The synthetic catalyst is a reduced Fischer-Tropsch synthesis catalyst, has higher Fischer-Tropsch synthesis reaction activity relative to a protective catalyst, and is required to keep the sulfur content of reaction gas at a lower level in order to avoid poisoning of the synthetic catalyst, i.e. a first-level Fischer-Tropsch synthesis system is required to reduce the S content in the synthetic gas to a set level, preferably, the iron-based catalyst requires the sulfur content to be lower than 0.1ppm, the cobalt-based catalyst requires the sulfur content to be lower than 5ppb, and most of the synthetic gas is converted into Fischer-Tropsch synthesis products under the action of the synthetic catalyst.
The reaction temperature of the reactor of the first-stage Fischer-Tropsch synthesis system is 200-280 ℃, and the reaction pressure is 2.0-5.0 MPa. The reactor form can be selected from a fixed bed, a slurry bed or a fluidized bed. Due to the high replacement frequency of the protective catalyst, a slurry bed or fluidized bed reactor which is more convenient for replacing the catalyst on line is preferably adopted. One or more reactors are connected in parallel. Gas at the outlet of the reactor is cooled by a series of heat exchange devices and subjected to gas-liquid separation by a separation device, most of high-carbon hydrocarbon, oxygen-containing organic matters and water are condensed to a liquid phase, the condensing temperature is preferably lower than the saturation temperature of water, and the separated tail gas enters a secondary Fischer-Tropsch synthesis system.
The tail gas of the first-stage Fischer-Tropsch synthesis system is a gas obtained by cooling and gas-liquid separating a product at the outlet of the reactor to remove most of high-carbon hydrocarbons, oxygen-containing organic matters and water, wherein the sulfur content of the gas meets the long-term use requirement of the Fischer-Tropsch synthesis catalyst, preferably, the sulfur content of the iron-based catalyst is required to be lower than 5ppm, and the sulfur content of the cobalt-based catalyst is required to be lower than 10 ppb.
The reactor of the two-stage Fischer-Tropsch synthesis system has the reaction temperature of 200-280 ℃, the reaction pressure of 2.0-5.0 MPa, and the reactor can be a fixed bed, a slurry bed or a fluidized bed. The reactor is one or more series or parallel reactors, preferably, the fixed bed reactor and the fluidized bed reactor are one or more parallel reactors, and the slurry bed reactor is one or more series or parallel reactors. After the gas at the outlet of the reactor is cooled by a series of heat exchange devices and gas-liquid separated by a separating device, hydrocarbon and reaction water rich in hydrocarbon gas and liquid can be obtained. And part of the hydrocarbon-rich gas is sent out of the system as product gas, and the other part of the hydrocarbon-rich gas is returned to the inlet of the reactor of the second-stage Fischer-Tropsch synthesis system through a circulating compressor, so that the conversion rate of the synthesis gas is further improved.
The product and the liquid product of the first-level Fischer-Tropsch synthesis system can be further processed by means of deep cooling, oil refining, synthesis and the like to obtain clean fuel and chemicals with high additional value.
The Fischer-Tropsch synthesis series system provided by the invention can be used for pretreating the synthesis gas with higher sulfur content by utilizing the combination of the waste catalyst and other catalysts or fine particles generated in the operation of the Fischer-Tropsch synthesis reactor, can further utilize the residual reaction activity of the waste catalyst, and can complete the chemical adsorption of sulfur during the Fischer-Tropsch synthesis, thereby reducing the consumption of the Fischer-Tropsch synthesis catalyst per ton of products and the energy consumption and material consumption in the process of desulfurizing the synthesis gas.
Compared with the prior art, the invention has the following advantages:
(1) the investment is low: the system can effectively reduce the load and equipment investment of the synthesis gas making device.
(2) The energy consumption is low: the process of desulfurizing the synthesis gas needs a large amount of electricity and public works, and the first-stage Fischer-Tropsch synthesis system can generate high-pressure steam by utilizing the characteristic of reaction heat release and can be used for power generation and stream heating.
(3) The material consumption is low: the waste catalyst is used for removing sulfur in the synthesis gas, so that the using amount of a desulfurizing agent can be effectively reduced.
(4) The catalyst consumption per ton of product is low: the system can secondarily utilize the waste catalyst generated in the Fischer-Tropsch synthesis production process to continuously produce Fischer-Tropsch synthesis products.
Drawings
FIG. 1 is a schematic diagram of a series system for Fischer-Tropsch synthesis.
The synthesis gas is 1, the first-stage Fischer-Tropsch synthesis system is 2, the first-stage Fischer-Tropsch synthesis tail gas is 3, the liquid hydrocarbon and the reaction water are 4, the second-stage Fischer-Tropsch synthesis system is 5, and the hydrocarbon-rich gas, the liquid hydrocarbon and the reaction water are 6.
Detailed Description
The method provided by the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited thereto, and specific devices such as reactors, heat exchangers, tanks, valves, motive equipment and the like, which are commonly used in the fischer-tropsch synthesis system, are omitted in the drawings in order to highlight the key idea of the present invention. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. All falling within the scope of the present invention.
As shown in figure 1, synthesis gas 1 enters a first-stage Fischer-Tropsch synthesis system 2, and a first-stage Fischer-Tropsch synthesis tail gas 3, liquid hydrocarbons and reaction water 4 are obtained after reaction, cooling and separation. The first-stage Fischer-Tropsch synthesis tail gas 2 enters a second-stage Fischer-Tropsch synthesis reaction system 5, and hydrocarbon-rich gas, liquid hydrocarbon and reaction water 6 are obtained after reaction, cooling, separation and tail gas circulation.
Wherein the first-stage Fischer-Tropsch synthesis system 2 and the second-stage Fischer-Tropsch synthesis reaction system 5 are Fischer-Tropsch synthesis systems commonly used in the field.
The following examples will further illustrate the system provided by the present invention, but the present invention is not limited thereto.
Example 1
In this example, the process shown in FIG. 1 was used, and the synthesis gas was coalObtained by coal gasification, water gas shift and decarburization, the coal consumption is 460t/h, and the synthesis gas quantity is 800000Nm3/h，H2the/CO ratio was 1.65 and the specific syngas specifications are shown in Table 1.
TABLE 1 syngas specification
| Flow rate Nm3/h | 800000 |
| Temperature of | 30 |
| Pressure MPaG | 3.07 |
| Composition of | vol％ |
| H2 | 59.50 |
| CO | 36.06 |
| CO2 | 2.40 |
| Ar | 0.14 |
| CH4 | 0.05 |
| N2 | 0.37 |
| Total sulfur | 2.05 |
The first-stage Fischer-Tropsch synthesis system consists of 1 slurry bed reactor with the diameter of 7m and matched heat exchange, synthetic wax filtration and gas-liquid separation devices. 100t of protective catalyst is filled in the reactor, and comprises 40 wt% of waste catalyst generated in the operation of a two-stage Fischer-Tropsch synthesis system and 60 wt% of iron oxide desulfurizer. The reactor was operated at 240 ℃ and at 3.0MPaG, and the synthetic wax in the reactor was withdrawn from the reactor bed and passed through a filtration unit to remove the catalyst therefrom. And (3) washing, heat exchange and gas-liquid separation are carried out on gas at the outlet of the reactor to obtain a liquid hydrocarbon product, reaction water and tail gas. Wherein the yield of the synthetic wax is 21t/h, the yield of the liquid hydrocarbon is 16t/h, the yield of the reaction water is 49t/h, and the specification of the tail gas is shown in Table 2.
TABLE 2 first order Fischer-Tropsch Synthesis System Tail gas Specification
| Flow rate Nm3/h | 614993 |
| Temperature of | 110 |
| Pressure MPaG | 2.85 |
| Composition of | vol％ |
| H2 | 60.51 |
| CO | 32.83 |
| CO2 | 2.40 |
| Ar | 0.14 |
| CH4 | 0.05 |
| N2 | 0.37 |
| ppmv | |
| Total sulfur | <0.1 |
And tail gas of the first-stage Fischer-Tropsch synthesis system enters a second-stage Fischer-Tropsch synthesis system. The second-stage Fischer-Tropsch synthesis system consists of 1 slurry bed reactor with the diameter of 10m, and a matched compressor, a heat exchange device, a synthetic wax filtering device and a gas-liquid separation device. 280t of synthetic catalyst is filled in the reactor, and the synthetic catalyst is reduced iron catalyst. The reactor was operated at 240 ℃ and 2.8MPaG, and the synthetic wax in the reactor was withdrawn from the reactor bed and passed through a filtration unit to remove the catalyst therefrom. And (3) washing, heat exchange and gas-liquid separation are carried out on gas at the outlet of the reactor to obtain a liquid hydrocarbon product, reaction water and hydrocarbon-rich gas. Wherein the yield of the synthetic wax is 50t/h, the yield of the liquid hydrocarbon is 42t/h, and the yield of the reaction water is 132 t/h. One part of the hydrocarbon-rich gas is returned to the inlet of the reactor through a compressor to increase the total conversion rate of CO, and the other part is sent out of the system.
The total yield of liquid hydrocarbon and synthetic wax of the system is 129t/h, the yield of reaction water is 181t/h, the consumption of catalyst per ton product is 1.1kg, the annual consumption of desulfurizer is 2800t, and the net energy consumption of a decarburization unit and a Fischer-Tropsch synthesis system is 219 MW.
Comparative example
This comparative example used the scheme shown in fig. 1, and the synthesis gas was obtained from coal gasification, water gas shift and purification, wherein purification was added with a low temperature methanol wash process to further remove sulfur from the synthesis gas based on the decarbonization of example 1. 460t/h of coal consumption and 780000Nm of synthetic gas3/h，H2the/CO ratio was 1.65 and the specific syngas specifications are shown in Table 3.
TABLE 3 syngas specification
| Flow rate Nm3/h | 78000 |
| Temperature of | 110 |
| Pressure MPaG | 2.85 |
| Composition of | vol％ |
| H2 | 61.68 |
| CO | 37.38 |
| CO2 | 0.37 |
| Ar | 0.14 |
| CH4 | 0.05 |
| N2 | 0.38 |
| ppmv | |
| Total sulfur | <0.1 |
Adopts a two-stage series Fischer-Tropsch synthesis system. The first-stage Fischer-Tropsch synthesis system consists of 1 slurry bed reactor with the diameter of 10m, and a matched compressor, a heat exchange device, a synthetic wax filtering device and a gas-liquid separation device. The reactor was loaded with 280t of iron-based catalyst. The reactor was operated at 240 ℃ and 2.8MPaG, and the synthetic wax in the reactor was withdrawn from the reactor bed and passed through a filtration unit to remove the catalyst therefrom. And (3) washing, heat exchange and gas-liquid separation are carried out on gas at the outlet of the reactor to obtain a liquid hydrocarbon product, reaction water and hydrocarbon-rich gas. Wherein the yield of the synthetic wax is 61t/h, the yield of the liquid hydrocarbon is 36t/h, and the yield of the reaction water is 140 t/h. A portion of the hydrocarbon-rich gas is returned to the reactor inlet via a compressor to increase the overall conversion of CO, and another portion is sent to a two-stage Fischer-Tropsch synthesis system.
The second-stage Fischer-Tropsch synthesis system consists of 1 slurry bed reactor with the diameter of 7m, and a matched compressor, a heat exchange device, a synthetic wax filtering device and a gas-liquid separation device. The reactor was charged with 160t of iron-based catalyst. The reactor was operated at 240 ℃ and 2.5MPaG, and the synthetic wax in the reactor was withdrawn from the reactor bed and passed through a filtration unit to remove the catalyst therefrom. And (3) washing, heat exchange and gas-liquid separation are carried out on gas at the outlet of the reactor to obtain a liquid hydrocarbon product, reaction water and hydrocarbon-rich gas. Wherein the yield of the synthetic wax is 10t/h, the yield of the liquid hydrocarbon is 22t/h, and the yield of the reaction water is 41 t/h. One part of the hydrocarbon-rich gas is returned to the inlet of the reactor through a compressor to increase the total conversion rate of CO, and the other part is sent out of the system.
The total yield of the synthetic wax and the liquid hydrocarbon of the system is 129t/h, the yield of reaction water is 181t/h, the consumption of a catalyst per ton product is 1.5kg, the annual consumption of a desulfurizer of a purifying device is 3100t, and the energy net consumption of a purifying unit and a Fischer-Tropsch synthesis system is 235 MW. It can be seen that, compared with the comparative example using the conventional technology, in example 1 using the present invention, under the same coal consumption and similar product yield conditions, the catalyst consumption per ton of product is reduced by 26.7%, the annual desulfurizer consumption is reduced by 9.7%, and the net energy consumption is reduced by 6.8%.
Claims (10)
1. The utility model provides a series system for ft synthesis, includes one-level ft synthesis system and second grade ft synthesis system, its characterized in that, one-level ft synthesis system and second grade ft synthesis system series connection, wherein the tail gas of one-level ft synthesis system gets into the reaction of second grade ft synthesis system, the reactor of one-level ft synthesis system in pack the protection catalyst, the reactor of second grade ft synthesis system in pack the synthetic catalyst.
2. A series system for fischer-tropsch synthesis according to claim 1, wherein the guard catalyst is a combination of one or more of: the catalyst comprises a Fischer-Tropsch synthesis waste catalyst, a reduced Fischer-Tropsch synthesis catalyst, a partially reduced Fischer-Tropsch synthesis catalyst, an oxidized Fischer-Tropsch synthesis catalyst and a desulfurizing agent.
3. A series system for fischer-tropsch synthesis as claimed in claim 2, wherein the spent fischer-tropsch synthesis catalyst is a catalyst which is replaced from the reactor during operation of the secondary fischer-tropsch synthesis system or other fischer-tropsch synthesis system.
4. A series system as claimed in claim 2, wherein the desulphurizing agent is a metal or metal compound particle which reacts with the sulphides in the synthesis gas to form solid sulphides.
5. A series system for fischer-tropsch synthesis according to claim 1, wherein the synthesis catalyst is a reduced fischer-tropsch synthesis catalyst.
6. The series system for Fischer-Tropsch synthesis of claim 1, wherein one or more reactors of the first-stage Fischer-Tropsch synthesis system are connected in parallel, and reactants at the outlet of the reactors are cooled and separated to obtain tail gas, and the tail gas enters the second-stage Fischer-Tropsch synthesis system.
7. A series system for Fischer-Tropsch synthesis according to claim 1 or claim 6, in which the tail gas from the first stage Fischer-Tropsch synthesis system is the gas obtained by cooling and gas-liquid separating the product at the outlet of the reactor to remove most of the higher hydrocarbons, oxygenated organics and water.
8. A series system for Fischer-Tropsch synthesis according to claim 1, wherein the reactors of the second stage Fischer-Tropsch synthesis system are one or more reactors connected in series or in parallel, and after cooling and separating the reactants at the outlet of the reactors, hydrocarbon-rich gas, liquid hydrocarbon and reaction water containing oxygen-containing organic matter are obtained, wherein one part of the hydrocarbon-rich gas returns to the inlet of the reactor, and the other part of the hydrocarbon-rich gas is sent out of the system.
9. The series system for Fischer-Tropsch synthesis of claim 1, wherein the reaction temperature of the reactor of the first-stage Fischer-Tropsch synthesis system is 200-280 ℃, and the reaction pressure is 2.0-5.0 MPa.
10. The series system for Fischer-Tropsch synthesis of claim 1, wherein the reaction temperature of the reactor of the two-stage Fischer-Tropsch synthesis system is 200-280 ℃ and the reaction pressure is 2.0-5.0 MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948438A (en) * | 2006-10-08 | 2007-04-18 | 神华集团有限责任公司 | Two stage Fischer-Tropsch synthesis method |
| CN111286354A (en) * | 2020-02-29 | 2020-06-16 | 上海兖矿能源科技研发有限公司 | Method and device for producing hydrocarbons by two-stage series connection of low-temperature Fischer-Tropsch and high-temperature Fischer-Tropsch |
| CN111944553A (en) * | 2020-08-10 | 2020-11-17 | 中科合成油技术有限公司 | Method for cascade Fischer-Tropsch synthesis reaction |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948438A (en) * | 2006-10-08 | 2007-04-18 | 神华集团有限责任公司 | Two stage Fischer-Tropsch synthesis method |
| CN111286354A (en) * | 2020-02-29 | 2020-06-16 | 上海兖矿能源科技研发有限公司 | Method and device for producing hydrocarbons by two-stage series connection of low-temperature Fischer-Tropsch and high-temperature Fischer-Tropsch |
| CN111944553A (en) * | 2020-08-10 | 2020-11-17 | 中科合成油技术有限公司 | Method for cascade Fischer-Tropsch synthesis reaction |
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