CN117899761A - Comprehensive utilization system and method for preparing hydrocarbon from synthesis gas - Google Patents
Comprehensive utilization system and method for preparing hydrocarbon from synthesis gas Download PDFInfo
- Publication number
- CN117899761A CN117899761A CN202211239054.4A CN202211239054A CN117899761A CN 117899761 A CN117899761 A CN 117899761A CN 202211239054 A CN202211239054 A CN 202211239054A CN 117899761 A CN117899761 A CN 117899761A
- Authority
- CN
- China
- Prior art keywords
- fischer
- gas
- slurry bed
- reactor
- synthesis
- 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.)
- Pending
Links
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 186
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 34
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 130
- 239000002002 slurry Substances 0.000 claims abstract description 102
- 239000000047 product Substances 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 150000001336 alkenes Chemical class 0.000 claims abstract description 64
- 238000000926 separation method Methods 0.000 claims abstract description 53
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 229910052742 iron Inorganic materials 0.000 claims description 38
- 229910001567 cementite Inorganic materials 0.000 claims description 27
- 239000012263 liquid product Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000001993 wax Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a comprehensive utilization system and a method for preparing hydrocarbon from synthesis gas, comprising the following steps: 1) Introducing synthesis gas into a slurry bed reactor A of a first Fischer-Tropsch synthesis unit, and carrying out gas-liquid-solid three-phase high-temperature high-pressure Fischer-Tropsch synthesis reaction under the action of a catalyst; 2) The gaseous reaction product in the slurry bed reactor A enters a gas-liquid separation unit A; 3) The non-condensable gaseous product enters an olefin separation unit A, and the separated tail gas enters a slurry bed reactor B of a second Fischer-Tropsch synthesis unit to continuously carry out Fischer-Tropsch synthesis reaction with hydrogen; 4) The gaseous reaction products in the slurry bed reactor B enter the gas-liquid separation unit B; 5) Non-condensable gaseous products enter a tail gas treatment unit to obtain alkene, alkane and CO 2. The invention can improve the processing capacity of the reactor, reduce the investment of the device, increase the yield of olefin with high added value, reduce the yield of products with low economic value such as CH 4, CO 2 and the like, and improve the comprehensive utilization efficiency of the synthesis gas.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch synthesis, in particular to a comprehensive utilization system and method for preparing hydrocarbon from synthesis gas.
Background
Fischer-Tropsch synthesis refers to the process by which synthesis gas is converted to products such as hydrocarbons, water, and oxygenates by a catalyst. The reactor used for Fischer-Tropsch synthesis can adopt a fixed bed reactor, a fluidized bed reactor and a slurry bed reactor, wherein the slurry bed reactor is a reactor commonly used for Fischer-Tropsch synthesis due to the characteristics of simple structure, easy temperature control and easy operation. During the reaction, gas enters the reactor from the bottom of the tower and is mixed with the Fischer-Tropsch synthesis heavy wax and solid catalyst particles in the bed layer to form a gas-liquid-solid three-phase reactor bed layer, unreacted gas and gas-phase products flow out from the top of the tower, and the gas can be used as recycle gas to enter the reactor again to participate in the Fischer-Tropsch synthesis reaction after being treated.
The conventional Fischer-Tropsch synthesis generally adopts 0.5-3.0MPa, most of which are 2.0-3.0MPa, and the temperature is about 220-270 ℃ for the Fischer-Tropsch synthesis reaction. The products include CH 4, C2-C4 gaseous hydrocarbons, oils and waxes, and small amounts of oxygen-containing organics, among others. Wherein the gaseous olefin with high added value accounts for relatively little, and the mass selectivity is generally between 1 and 3 percent. Compared with the conventional Fischer-Tropsch synthesis, the Fischer-Tropsch synthesis method has the advantages that the high temperature and high pressure (the high temperature is 260-290 ℃ and the high pressure is 6-12 MPa) Fischer-Tropsch synthesis method can improve the conversion rate of synthesis gas, increase the treatment capacity of a reactor and increase the oil product yield. But the selectivity of CO 2 and CH 4 is too high, which greatly reduces the comprehensive utilization efficiency of the synthesis gas.
CN 101955788A provides a two-stage fischer-tropsch synthesis in series, in which the CO conversion in the first stage reactor is only about 50%, the total CO conversion is only about 91%, the CO 2 selectivity is up to 25.3%, the CH 4 selectivity is up to 6.7%, and the oil yield is low. While the main products described in this document are oils, no reference is made to the production of olefins.
In addition, in the prior art, no matter the conventional Fischer-Tropsch synthesis, the high-temperature high-pressure Fischer-Tropsch synthesis or the two-section serial Fischer-Tropsch synthesis scheme is adopted, the reacted synthesis gas is recycled into the reactor to improve the conversion rate of the synthesis gas, so that the oil product yield is improved, the utilization rate of the reactor is greatly reduced, the device scale is larger, and the treatment capacity of the reactor is lower.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a comprehensive utilization system and method for hydrocarbon production from synthesis gas, which can increase the throughput of a reactor, increase the yield of olefins with high added value, reduce the yield of products with low economic value such as CH 4 and CO 2, and increase the comprehensive utilization efficiency of synthesis gas.
To achieve the above object, according to a first aspect of the present invention, there is provided a comprehensive utilization system for producing hydrocarbons from synthesis gas, comprising:
a) A first fischer-tropsch synthesis unit comprising:
at least one slurry bed reactor A having a synthesis gas bottom inlet, a gaseous product top outlet and a Fischer-Tropsch wax middle or lower outlet, wherein a gas-liquid-solid three-phase reactant stream is subjected to a high temperature and high pressure Fischer-Tropsch synthesis reaction in the reactor under the action of a catalyst;
At least one gas-liquid separation unit a for separating the gaseous product into a condensable liquid product and a non-condensable gaseous product; and
At least one olefin separation unit for separating the non-condensable gaseous product and/or the condensable liquid product to obtain olefin, alkane and tail gas;
b) A second fischer-tropsch synthesis unit comprising:
at least one slurry bed reactor B having a synthesis gas bottom inlet, a gaseous product top outlet and a Fischer-Tropsch wax middle or lower outlet, wherein a gas-liquid-solid three-phase reactant stream is subjected to a Fischer-Tropsch synthesis reaction in the reactor under the action of a catalyst;
At least one gas-liquid separation unit B for separating the gaseous product into a condensable liquid product and a non-condensable gaseous product; and
At least one tail gas treatment unit for treating the non-condensable gaseous products to produce olefins, paraffins, and CO 2;
Wherein the tail gas of the first Fischer-Tropsch synthesis unit and the supplementary hydrogen enter a slurry bed reactor B of the second Fischer-Tropsch synthesis unit for reaction.
The second aspect of the invention provides a comprehensive utilization method for preparing hydrocarbon from synthesis gas, comprising the following steps:
1) Introducing synthesis gas comprising CO and H 2 into a slurry bed reactor A of a first Fischer-Tropsch synthesis unit, and carrying out gas-liquid-solid three-phase Fischer-Tropsch synthesis reaction under the action of a catalyst; the reaction temperature is 260-350 ℃, and the reaction pressure is 2-6Mpa;
2) The gaseous reaction product in the slurry bed reactor A enters the gas-liquid separation unit A and is separated into condensable liquid product and non-condensable gaseous product therein;
3) The non-condensable gaseous product enters an olefin separation unit A to separate alkane and olefin in tail gas, the separated tail gas enters a slurry bed reactor B of a second Fischer-Tropsch synthesis unit, and the separated tail gas and hydrogen provided by the outside continue to carry out Fischer-Tropsch synthesis reaction; the reaction temperature is 220-280 ℃, and the reaction pressure is 2-4MPa;
4) The gaseous reaction products in the slurry bed reactor B enter the gas-liquid separation unit B and are separated therein into condensable liquid products and non-condensable gaseous products;
5) The non-condensable gaseous products enter a tail gas treatment unit and are treated to obtain alkene, alkane and CO 2.
According to the method of the invention, the tail gas obtained after the tail gas treatment unit is treated is taken as recycle gas to enter the slurry bed reactor B for continuously carrying out Fischer-Tropsch synthesis reaction.
Compared with the prior art, the invention has the following advantages:
The invention introduces the synthesis gas comprising CO and H 2 into the slurry bed reactor A of the first Fischer-Tropsch synthesis unit, the gas-liquid-solid three-phase reactant flow is reacted at high temperature and high pressure under the action of a catalyst in the reactor, then the tail gas (mainly comprising unreacted CO and H 2 and a small amount of CH 4 and CO 2) in the first Fischer-Tropsch synthesis unit and the externally provided hydrogen are introduced into the slurry bed reactor B of the first Fischer-Tropsch synthesis unit, and the gas-liquid-solid three-phase reactant flow is not returned into the slurry bed reactor A, and is reacted at conventional temperature and pressure under the action of the catalyst in the reactor. In the product of the first Fischer-Tropsch synthesis unit, the single pass conversion rate (also the total conversion rate) of CO is more than 75%, the mass selectivity of the olefin product is more than 40%, and as the synthesis gas passes through one pass, compared with a conventional slurry bed reactor with the same size, the treatment capacity of the synthesis gas and the yield of the Fischer-Tropsch synthesis product are greatly improved, namely if the synthesis gas with the same scale is treated, the device of the invention has smaller scale and lower investment.
In the second Fischer-Tropsch synthesis unit, as only the tail gas of the first Fischer-Tropsch synthesis unit is treated, the synthesis gas amount is lower than 30% of that of the first Fischer-Tropsch synthesis unit, the conventional Fischer-Tropsch synthesis reaction can be adopted, the total conversion rate of CO is more than 97%, and the total conversion rate of the synthesis gas (CO+H 2) is more than 90%.
Conventional fischer-tropsch catalysts typically have a high selectivity for CO 2 or CH 4, a byproduct, typically 25% -45% of the carbon monoxide of the conversion feedstock. One of the main reasons is that the catalyst contains a large amount of Fe impurities, which are various Fe (elemental) containing phase components other than iron carbide. The catalyst adopted by the invention only contains 0-5mol percent of Fe impurity, and the balance is pure phase Fe, so that the selectivity of CO 2 or CH 4 byproducts is greatly reduced, and the yield of target products is improved.
In addition, the first Fischer-Tropsch synthesis unit can obtain high-value-added olefins through the olefin separation unit, and the tail gas treatment of the second Fischer-Tropsch synthesis unit can also obtain high-value-added olefins, so that compared with a small amount of olefins in 200 ten thousand tons of oil products produced in a conventional Fischer-Tropsch year, the yield of olefins in 200 ten thousand tons of oil products is more than 60 ten thousand tons, and the economic value is remarkably improved.
In conclusion, the invention can improve the treatment capacity of the reactor, reduce the scale and investment of the reaction device, increase the yield of olefin with high added value, reduce the yield of products with low economic value such as CH 4, CO 2 and the like, and improve the comprehensive utilization efficiency of the synthesis gas.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a schematic diagram of an exemplary integrated utilization system for producing hydrocarbons from synthesis gas.
The labels are described as 1.1-slurry bed reactor A, 1.2-gas-liquid separation unit A, 1.3-olefin separation unit (1.31-olefin separation unit A, 1.32-olefin separation unit B), 1.4-inner filter A, 2.1-slurry bed reactor B, 2.2-gas-liquid separation unit B, 2.3-tail gas treatment unit, 2.4-inner filter B.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the present invention, unless otherwise specified, terms such as "upper, lower, top, and bottom" and "upper, lower, top, and bottom" are used generally to refer to orientations in the installed and used state. "inner and outer" means inner and outer relative to the contour of the respective parts themselves.
In the following examples and comparative examples,
In the Fischer-Tropsch synthesis:
carrying out gas chromatographic analysis (Agilent 6890 gas chromatography) on the product obtained by the reaction;
The reaction effect is calculated by the following formula:
CO 2% selectivity = [ CO 2 moles in the output/(CO moles in the feed-CO moles in the output) ] × 100%;
CH 4% selectivity = [ CH 4 moles in the output/(moles CO in the input—moles CO in the output) ] × 100%;
CO conversion= (1- [ moles of CO in the effluent/(moles of CO in the feed) ]) x 100%;
the invention provides a comprehensive utilization system for preparing hydrocarbon from synthesis gas, which comprises:
a) A first fischer-tropsch synthesis unit comprising:
at least one slurry bed reactor A having a synthesis gas bottom inlet, a gaseous product top outlet and a Fischer-Tropsch wax middle or lower outlet, wherein a gas-liquid-solid three-phase reactant stream is subjected to a high temperature and high pressure Fischer-Tropsch synthesis reaction in the reactor under the action of a catalyst;
At least one gas-liquid separation unit a for separating the gaseous product into a condensable liquid product and a non-condensable gaseous product; and
At least one olefin separation unit for separating the non-condensable gaseous product and/or the condensable liquid product to obtain olefin, alkane and tail gas;
b) A second fischer-tropsch synthesis unit comprising:
at least one slurry bed reactor B having a synthesis gas bottom inlet, a gaseous product top outlet and a Fischer-Tropsch wax middle or lower outlet, wherein a gas-liquid-solid three-phase reactant stream is subjected to a Fischer-Tropsch synthesis reaction in the reactor under the action of a catalyst;
At least one gas-liquid separation unit B for separating the gaseous product into a condensable liquid product and a non-condensable gaseous product; and
At least one tail gas treatment unit for treating the non-condensable gaseous products to produce olefins, paraffins, and CO 2;
Wherein the tail gas of the first Fischer-Tropsch synthesis unit (mainly comprising unreacted CO and H 2 and a small amount of CH 4 and CO 2) and make-up hydrogen enter a slurry bed reactor B of the second Fischer-Tropsch synthesis unit for reaction.
In the present invention, the gas-liquid separation unit a or the gas-liquid separation unit B may be a gas-liquid separator, a gas-liquid separation tank, and/or a hydrocyclone. Further, the gas-liquid separator tank may be a high temperature gas-liquid separator tank, a low temperature gas-liquid separator tank, a high pressure gas-liquid separator tank, and/or a low pressure gas-liquid separator tank. In order to separate the liquid and gaseous components in the product, a gas-liquid separation unit a is preferably provided at the outlet of the high temperature, high pressure slurry bed reactor a.
In the present invention, the number of the olefin separation units may be plural, and in a specific embodiment, an olefin separation unit a may be provided for separating olefins and paraffins in the non-condensable gaseous product, so as to obtain tail gas and enter the second fischer-tropsch synthesis unit; an olefin separation unit B may also be provided for separating olefins and paraffins from the condensable liquid products (e.g. oils). The olefin separation unit refers to an existing olefin separation plant configuration.
In the invention, oil products are obtained at a plurality of process points, for example, an inner filter A is arranged in a slurry bed reactor A, an inner filter B is arranged in a slurry bed reactor B, and solid catalyst in Fischer-Tropsch wax is filtered out to obtain the oil products. The outlets at the lower parts of the gas-liquid separation unit A and the gas-liquid separation unit B can also obtain oil products. Likewise, olefins may be obtained at a plurality of process points, for example, by passing through the olefin separation unit a, the olefin separation unit B, and the off-gas treatment unit, respectively.
In one embodiment of the invention, the system may further comprise auxiliary CO-equipment such as a supercharger, a preheating furnace, a fine desulfurization reactor, a heat exchanger, a filter and/or a CO 2 removal unit. The above devices are all commonly used devices in the fischer-tropsch synthesis reaction, and the installation position and the specific structure can be determined according to the requirements, and are not described again.
Based on the system, the invention also provides a comprehensive utilization method for preparing hydrocarbon from the synthesis gas, which comprises the following steps:
1) Introducing synthesis gas comprising CO and H 2 into a slurry bed reactor A of a first Fischer-Tropsch synthesis unit, and carrying out gas-liquid-solid three-phase Fischer-Tropsch synthesis reaction under the action of a catalyst; the reaction temperature is 260-350 ℃, and the reaction pressure is 2-6Mpa;
2) The gaseous reaction product in the slurry bed reactor A enters the gas-liquid separation unit A and is separated into condensable liquid product and non-condensable gaseous product therein;
3) The non-condensable gaseous product enters an olefin separation unit A to separate alkane and olefin in tail gas, the separated tail gas enters a slurry bed reactor B of a second Fischer-Tropsch synthesis unit, and the separated tail gas and hydrogen provided by the outside continue to carry out Fischer-Tropsch synthesis reaction; the reaction temperature is 220-280 ℃, and the reaction pressure is 2-4MPa;
4) The gaseous reaction products in the slurry bed reactor B enter the gas-liquid separation unit B and are separated therein into condensable liquid products and non-condensable gaseous products;
5) The non-condensable gaseous products enter a tail gas treatment unit and are treated to obtain alkene, alkane and CO 2.
In the present invention, preferably, the slurry bed reactor A in step 1) is operated at a reaction temperature of 260 to 350 ℃, such as 260 ℃,265 ℃,270 ℃,275 ℃,280 ℃,285 ℃, 290 ℃,295 ℃,300 ℃,305 ℃,310 ℃,315 ℃,320 ℃,325 ℃,330 ℃,335 ℃,340 ℃,345 ℃,350 ℃ or other values within the range, the reaction temperature may be further 260 to 330 ℃, the reaction pressure is 2 to 6MPa, such as 2MPa,3MPa,4MPa,5MPa,6MPa, etc. or other values within the range; reactor inlet air velocity: 0.1-0.4 m/s; space velocity of fresh syngas: 2000-25000 square per ton of catalyst per hour, e.g., 2000, 5000, 8000, 10000, 12000, 15000, 18000, 20000, 22000, 25000, etc. square per ton of catalyst per hour or other values within this range; reactor slurry bed solids content: 10-30 wt%; synthesis gas H 2/CO (volume): 1-2.5.
More preferably, the operating parameters of slurry bed reactor a in step 1) are reaction temperature: 280-310 ℃; reaction pressure: 2.5-4MPa; reactor inlet air velocity: 0.15-0.3 m/s; space velocity of fresh syngas: 3000-23000 standard/ton catalyst/hr; reactor slurry bed solids content: 10-25 wt%; synthesis gas H 2/CO (volume): 1.5-2.0.
In one embodiment of the invention, the catalyst employed in step 1) is preferably a supported χ -iron carbide composition comprising 55-90% by weight of the support and 10-45% by weight of the iron component, wherein the iron component comprises 95-100mol% χ -iron carbide and 0-5mol% Fe-containing impurities, based on the total amount of the iron component, which are iron-containing species other than χ -iron carbide, as described in particular in CN 112569983A.
More preferably, the above catalyst comprises 60-85 wt% of the support and 15-40 wt% of the iron component, wherein the iron component comprises 97-100mol% pure χ -iron carbide and 0-3mol% Fe-containing impurities, based on the total amount of the iron component, which are iron-containing species other than χ -iron carbide.
In one embodiment of the invention, the catalyst employed in step 1) is preferably a precipitated χ -iron carbide-containing composition comprising 95-100mol% precipitated χ -iron carbide and 0-5mol% Fe-containing impurities, which are Fe-containing species other than χ -iron carbide, as described in particular with reference to CN 112569992A.
In one embodiment of the invention, the catalyst employed in step 1) is preferably a χ -containing iron carbide composition comprising 95-100mol% χ -iron carbide and 0-5mol% Fe-containing impurities, which are iron-containing species other than χ -iron carbide, as described in particular with reference to CN 112569985A.
In the present invention, the operating parameters of the slurry bed reactor B in step 3) are the reaction temperature: 220-270 ℃; reaction pressure: 2-3MPa; reactor inlet air velocity: 0.1-0.4 m/s; space velocity of fresh syngas: 2000-10000 standard per ton of catalyst per hour; reactor slurry bed solids content: 5-20 wt%; synthesis gas H 2/CO (volume): 1-2.5.
In the invention, tail gas of a first Fischer-Tropsch synthesis unit (such as tail gas from an olefin separation unit A) and external supplementary hydrogen are fed into a slurry bed reactor B, the total conversion rate of synthesis gas in a second Fischer-Tropsch synthesis unit reaches more than 97%, and a catalyst is a conventional Fischer-Tropsch synthesis catalyst. Preferably, the tail gas obtained after the tail gas treatment unit is treated is taken as recycle gas to enter the slurry bed reactor B again for continuously carrying out Fischer-Tropsch synthesis reaction.
In the present invention, the synthesis gas typically should be preheated and finely desulphurised as feedstock before entering the slurry bed reactor.
In the present invention, the reaction heat may be extracted from the slurry bed reactor and/or the reaction product, thereby generating high-grade steam at high temperature and high pressure.
In the product of the first Fischer-Tropsch synthesis unit, the conversion rate of CO is more than 75%, and the mass selectivity of olefin products is more than 40%. Since the synthesis gas can be passed through in a single pass, the size of the slurry bed reactor a can be smaller. For example, the slurry bed reactor for producing 50 ten thousand tons of oil products in a conventional Fischer-Tropsch synthesis year needs about 10m in diameter. Whereas in the present invention the first Fischer-Tropsch synthesis unit employs a slurry bed reactor A of the same diameter 10m, the synthesis gas throughput is 2-4 times that of conventional Fischer-Tropsch synthesis. The yield of Fischer-Tropsch synthesis products is correspondingly improved.
In addition, since the synthesis gas in the first Fischer-Tropsch synthesis unit is passed in a single pass, the size or number of reactors may be reduced. For example, in the case of 200 ten thousand tons of oil produced in a conventional Fischer-Tropsch synthesis year, 4 slurry bed reactors with diameters of about 10m and corresponding 4 sets of equipment, such as a supercharger, a recycle compressor, a heat exchanger, a filter, a CO 2 removal device, and the like, are required. Whereas in the present invention only two slurry bed reactors of diameter 10m are required, with 1 set of CO-equipment such as a booster, recycle compressor, heat exchanger, filter and/or CO 2 removal unit, etc. at the same synthesis gas throughput. Compared with the conventional Fischer-Tropsch synthesis, the investment cost of the method is reduced by more than one time. Moreover, compared with the conventional Fischer-Tropsch year for producing very small amount of olefin in 200 ten thousand tons of oil products, the invention has the advantages that the yield of olefin in 200 ten thousand tons of oil products is more than 60 ten thousand tons per year, and the economic value is obvious.
In the second Fischer-Tropsch synthesis unit, as only the tail gas of the first Fischer-Tropsch synthesis unit is treated, the synthesis gas amount is lower than 30% of that of the first Fischer-Tropsch synthesis unit, and the total conversion rate of CO can reach more than 97% by adopting a conventional Fischer-Tropsch synthesis process, and the total conversion rate of synthesis gas (CO+H 2) is more than 90%. The product is mainly oil products with economic value.
In the present invention, for the sake of description, the first Fischer-Tropsch synthesis unit will be referred to simply as the first stage and the second Fischer-Tropsch synthesis unit will be referred to simply as the second stage.
The invention is further described below with the aid of detailed exemplary embodiments, which do not constitute any limitation of the invention.
Example 1
The Fischer-Tropsch synthesis process is carried out according to the process flow of the slurry bed reactor Fischer-Tropsch synthesis system illustrated in FIG. 1, so as to realize the comprehensive utilization of the synthesis gas of the high-yield and high-added-value hydrocarbons.
The diameter of the slurry bed reactor A1.1 in the first stage is 10m, the height is 60m, and the catalyst inventory of the reactor is 180 tons; the slurry bed reactor B2.1 in the second stage has a diameter of 10m and a catalyst inventory of 70 tons.
Fresh syngas throughput: 125 Mo Biaofang/hr; olefin yield: 55 ten thousand tons/year; the annual production of the remaining c5+ hydrocarbon liquid hydrocarbons is about 115 ten thousand tons per year; time of year start: 8000 hours.
The slurry bed reactor A1.1 of the first stage has the following operating parameters and reaction pressure: 3.5MPa, reaction temperature: 290 ℃ and the air speed at the inlet of the reactor: 0.25 m/s; space velocity of fresh syngas: 15000 standard/ton catalyst/hr; reactor slurry bed solids content: 25% by weight; synthesis gas H 2/CO (volume ratio): 2.0.
The slurry bed reactor B2.1 of the second stage has the following operating parameters and reaction pressure: 3.0MPa, reaction temperature: 260 ℃, reactor inlet air speed: 0.2 m/s; space velocity of fresh syngas: 5000 standard per ton of catalyst per hour; reactor slurry bed solids content: 10% by weight; synthesis gas H 2/CO (volume ratio): 1.7.
Catalyst of the first stage: the catalyst prepared in example 1 of the process described in CN112569983a was used, namely:
A supported χ -iron carbide composition comprising 70% by weight of a carrier and 30% by weight of an iron component, wherein the iron component comprises 97mol% χ -iron carbide and 3mol% Fe-containing impurities, based on the total amount of the iron component. The catalyst can continuously and stably perform Fischer-Tropsch synthesis reaction, and has extremely low CO 2 selectivity and high selectivity of hydrocarbon effective products.
Catalyst of the second fischer-tropsch synthesis unit: a conventional Fischer-Tropsch catalyst, such as the catalyst prepared in example 1 of the method in CN101767010B, is a precipitated iron type 100Fe-5Cu-3K-16SiO 2 (mass ratio) microspherical Fischer-Tropsch catalyst prepared by a spray drying method.
When the reactor starts to operate, the synthesis gas comprising H 2 and CO enters the slurry bed reactor A1.1 of the first stage, and the tail gas passes through the gas-liquid separation unit A1.2 and the olefin separation unit A1.31 and then enters the slurry bed reactor B2.1 of the second stage to be reacted with the complementary hydrogen. Slurry bed reactor a 1.1 and slurry bed reactor B2.1 were continuously operated under the above-described operating conditions and operating parameters for a total of 500 hours.
The total conversion rate of CO in the synthesis gas is 97.5% and the total conversion rate of (H 2 +CO) is 91% in the two stages of the process. The mass selectivity of olefin with high added value is 33%, the selectivity of CO 2 is 18%, the selectivity of methane is 4.5%, and meanwhile, the byproduct is saturated steam with the pressure of 3.0MPa and the temperature of 200 ℃; 40% by mass of light oil, 35% by mass of heavy oil and 25% by mass of Fischer-Tropsch wax in the liquid hydrocarbon product; fischer-Tropsch synthesis water contains about 4% of Fischer-Tropsch synthesis byproducts, which are organic oxygenates.
This example requires 2 slurry bed reactors of diameter 10m in series, so 1 set of equipment including a booster, a preheating furnace, a fine desulfurization reactor, a recycle compressor, a heat exchanger, a filter, and/or a CO 2 removal unit, etc., is required, and the overall investment is expected to be no more than 100 gigabytes.
Example 2
The Fischer-Tropsch synthesis process is carried out according to the process flow of the slurry bed reactor Fischer-Tropsch synthesis system illustrated in FIG. 1, so as to realize the comprehensive utilization of the synthesis gas of the high-yield and high-added-value hydrocarbons.
The diameter of the slurry bed reactor A1.1 in the first stage is 10m, the height is 60m, and the catalyst inventory of the reactor is 180 tons; the slurry bed reactor B2.1 in the second stage has a diameter of 10m and a catalyst inventory of 70 tons.
Fresh syngas throughput: 125 Mo Biaofang/hr; olefin yield: 55 ten thousand tons/year; the annual production of the remaining c5+ hydrocarbon liquid hydrocarbons is about 115 ten thousand tons per year; time of year start: 8000 hours.
The slurry bed reactor A1.1 of the first stage has the following operating parameters and reaction pressure: 3.0MPa, reaction temperature: 305 ℃, reactor inlet superficial gas velocity: 0.25 m/s; space velocity of fresh syngas: 15000 standard/ton catalyst/hr; reactor slurry bed solids content: 25% by weight; synthesis gas H 2/CO (volume ratio): 2.0.
The slurry bed reactor B2.1 of the second stage has the following operating parameters and reaction pressure: 3.0MPa, reaction temperature: 260 ℃, reactor inlet air speed: 0.2 m/s; space velocity of fresh syngas: 5000 standard per ton of catalyst per hour; reactor slurry bed solids content: 10% by weight; synthesis gas H 2/CO (volume ratio): 1.7.
Catalyst of the first stage: the catalyst prepared in example 1 of the process described in CN112569983a was used, namely:
A supported χ -iron carbide composition comprising 70% by weight of a carrier and 30% by weight of an iron component, wherein the iron component comprises 97mol% χ -iron carbide and 3mol% Fe-containing impurities, based on the total amount of the iron component. The catalyst can continuously and stably perform Fischer-Tropsch synthesis reaction, and has extremely low CO 2 selectivity and high selectivity of hydrocarbon effective products.
Catalyst of the second fischer-tropsch synthesis unit: a conventional Fischer-Tropsch catalyst, such as the catalyst prepared in example 1 of the method in CN101767010B, is a precipitated iron type 100Fe-5Cu-3K-16SiO 2 (mass ratio) microspherical Fischer-Tropsch catalyst prepared by a spray drying method.
When the reactor starts to operate, the synthesis gas comprising H 2 and CO enters the slurry bed reactor A1.1 of the first stage, and the tail gas passes through the gas-liquid separation unit A1.2 and the olefin separation unit A1.31 and then enters the slurry bed reactor B2.1 of the second stage to be reacted with the complementary hydrogen. Slurry bed reactor a 1.1 and slurry bed reactor B2.1 were continuously operated under the above-described operating conditions and operating parameters for a total of 500 hours.
The total conversion rate of CO in the synthesis gas is 97.3% and the total conversion rate of (H 2 +CO) is 91.2% in the two stages of the process. The mass selectivity of olefin with high added value is 34%, the selectivity of CO 2 is 17%, the selectivity of methane is 4.3%, and meanwhile, the byproduct is saturated steam with the pressure of 3.0MPa and the temperature of 200 ℃; 43% by mass of light oil, 32% by mass of heavy oil and 25% by mass of Fischer-Tropsch wax in the liquid hydrocarbon product; fischer-Tropsch synthesis water contains about 4% of Fischer-Tropsch synthesis byproducts, which are organic oxygenates.
This example requires 2 slurry bed reactors of diameter 10m in series, so 1 set of equipment including a booster, a preheating furnace, a fine desulfurization reactor, a recycle compressor, a heat exchanger, a filter, and/or a CO 2 removal unit, etc., is required, and the overall investment is expected to be no more than 100 gigabytes.
Comparative example 1
The comparative example uses a conventional Fischer-Tropsch synthesis process.
Fresh syngas throughput as in example 1: 125 Mo Biaofang/hr. 4 slurry bed reactors with the diameter of 10m are required to be connected in parallel (the diameter of the current largest-scale Fischer-Tropsch synthesis layer slurry bed reactor in China is 10 m), and the height is 60m. The catalyst inventory required 300 tons.
The annual output of oil products is about 170 ten thousand tons; time of year start: 8000 hours. According to the calculation, the theoretical olefin yield is 6 ten thousand tons/year, and the separation cost is too high, and the economy is not improved, so that the olefin is not separated.
The slurry bed reactor operating parameters were as follows: reaction pressure: 3.0MPa, reaction temperature: 260 ℃, reactor inlet air speed: 0.2 m/s; space velocity of fresh syngas: 5000 standard per ton of catalyst per hour; reactor slurry bed solids content: 10% by weight; synthesis gas H 2/CO (volume): 1.7.
The catalyst is a conventional Fischer-Tropsch synthesis catalyst prepared by adopting a method in CN101767010B, namely a precipitated iron type 100Fe-5Cu-3K-16SiO 2 microspherical Fischer-Tropsch synthesis catalyst prepared by adopting a spray drying method.
When the reactor starts to operate, the synthesis gas comprising H 2 and CO enters the slurry bed reactor, and tail gas is circularly enters the reactor for continuous reaction after gas-liquid separation. The 4 reactors were operated continuously for 500 hours under the above operating conditions and operating parameters.
Wherein the CO conversion rate in the synthesis gas is 97%, the total (H 2 +CO) conversion rate is 90%, the CO 2 selectivity is 22%, the methane selectivity is 4%, and meanwhile, the byproduct is saturated steam with the pressure of 3.0MPa and the temperature of 200 ℃.
15% By mass of light oil, 25% by mass of heavy oil and 60% by mass of Fischer-Tropsch wax in the liquid hydrocarbon product; fischer-Tropsch synthesis water contains 3% of Fischer-Tropsch synthesis byproducts, which are organic oxygenates.
This comparative example requires 4 slurry bed reactors of diameter 10m in parallel and 4 sets of equipment including a booster, a preheating furnace, a fine desulfurization reactor, a recycle compressor, a heat exchanger, a filter, and/or a CO 2 removal unit, etc., with an overall investment of over 200 gigabytes expected.
Comparison of the process conditions of inventive example 1 with comparative example 1 table 1 below:
TABLE 1
Comparative example 2
The comparative example uses the high temperature and high pressure Fischer-Tropsch synthesis process in CN 103170284A.
Fresh syngas throughput as in example 1: 125 Mo Biaofang/hr. 4 slurry bed reactors with the diameter of 10m are required to be connected in parallel (the diameter of the current largest-scale Fischer-Tropsch synthesis layer slurry bed reactor in China is 10 m), and the height is 60m. The catalyst inventory required 1000 tons.
The annual output of oil products is about 200 ten thousand tons; time of year start: 8000 hours. According to the calculation, the theoretical yield of olefin is 9 ten thousand tons/year, and the separation cost is too high, and the economy is not improved, so that the olefin is not separated.
The slurry bed reactor operating parameters were as follows: reaction pressure: 7.5MPa, reaction temperature: 270 ℃, reactor inlet air speed: 0.2 m/s; space velocity of fresh syngas: 5000 standard per ton of catalyst per hour; reactor slurry bed solids content: 15% by weight; synthesis gas H 2/CO (volume): 1.7.
The catalyst used was a catalyst prepared using CN 103170284A: namely, the precipitated iron type 100Fe-3Cu-4K-12SiO 2 (mass ratio) microspherical Fischer-Tropsch synthesis catalyst prepared by a spray drying method has the particle size of 20-100 microns, wherein the catalyst particles with the particle size of 30-80 microns account for more than 95%, the average particle size is about 75 microns, and the density is about 0.75g/cm 3.
When the reactor starts to operate, the synthesis gas comprising H 2 and CO enters the slurry bed reactor, and tail gas is circularly enters the reactor for continuous reaction after gas-liquid separation. The 4 reactors were operated continuously for 500 hours under the above operating conditions and operating parameters.
In this comparative example, the CO conversion in the synthesis gas was 97%, the total (H 2 +co) conversion was 90%, the CO 2 selectivity was 25%, the methane selectivity was 5%, and the by-product pressure was 3.0MPa and the temperature was 200 ℃ saturated steam.
This comparative example requires 4 slurry bed reactors of diameter 10m in parallel and four sets of equipment including a booster, a preheater, a fine desulfurization reactor, a recycle compressor, a heat exchanger, a filter, and/or a CO 2 removal unit, etc., with an overall investment of over 200 gigabytes estimated.
Comparison of the process conditions of inventive example 1 and comparative example 2 table 2 below:
TABLE 2
Comparative example 3
The present comparative example uses the Fischer-Tropsch synthesis process in CN 101955788A, i.e., a two-stage series Fischer-Tropsch synthesis process.
Fresh syngas throughput as in example 1: 125 Mo Biaofang/hr. 4 sets of slurry bed reactors with the diameter of 5m and 7m are required to be connected in parallel, and the total amount of 8 slurry bed reactors is required to be 400 tons of catalyst inventory.
The annual output of the oil product is about 160 ten thousand tons; time of year start: 8000 hours. Because of the low olefin content, the theoretical olefin yield is 4 ten thousand tons per year, calculated, and because of the high separation cost and no economy, the olefin is not separated.
The slurry bed reactor operating parameters were as follows: reaction pressure: 2.8MPa, reaction temperature: 255 ℃, air speed at the inlet of the reactor: 0.15 m/s; space velocity of fresh syngas: 4000 square per ton of catalyst per hour; reactor slurry bed solids content: 10% by weight; synthesis gas H2/C0 (volume): 1.7;
The catalyst is a conventional Fischer-Tropsch synthesis catalyst prepared by adopting a method in CN101767010B, namely a precipitated iron type 100Fe-5Cu-3K-16SiO 2 microspherical Fischer-Tropsch synthesis catalyst prepared by adopting a spray drying method.
In this comparative example, the CO conversion in the synthesis gas was 91.7%, the total (H 2 +co) conversion was 83%, the CO 2 selectivity was 25.3%, the methane selectivity was 6.7%, and the liquid hydrocarbon yield was nearly 160 ten thousand tons/year, with a theoretical yield of olefins of only 5 ten thousand tons/year.
In addition, in this comparative example, 4 sets of 8 slurry bed reactors in total, and four sets of equipment including a booster, a preheating furnace, a fine desulfurization reactor, a recycle compressor, a heat exchanger, a filter, and/or a CO 2 removal unit, etc., are required, and the overall investment is expected to be more than 200 gigabytes.
Comparison of the process conditions of inventive example 1 with comparative example 3 the following table 3:
TABLE 3 Table 3
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. Not all embodiments are exhaustive. All obvious variations or modifications which come within the spirit of the invention are desired to be protected.
Claims (10)
1. A comprehensive utilization system for preparing hydrocarbon from synthesis gas is characterized in that: comprising the following steps:
a) A first fischer-tropsch synthesis unit comprising:
at least one slurry bed reactor A having a synthesis gas bottom inlet, a gaseous product top outlet and a Fischer-Tropsch wax middle or lower outlet, wherein a gas-liquid-solid three-phase reactant stream is subjected to a high temperature and high pressure Fischer-Tropsch synthesis reaction in the reactor under the action of a catalyst;
At least one gas-liquid separation unit a for separating the gaseous product into a condensable liquid product and a non-condensable gaseous product; and
At least one olefin separation unit for separating the non-condensable gaseous product and/or the condensable liquid product to obtain olefin, alkane and tail gas;
b) A second fischer-tropsch synthesis unit comprising:
at least one slurry bed reactor B having a synthesis gas bottom inlet, a gaseous product top outlet and a Fischer-Tropsch wax middle or lower outlet, wherein a gas-liquid-solid three-phase reactant stream is subjected to a Fischer-Tropsch synthesis reaction in the reactor under the action of a catalyst;
At least one gas-liquid separation unit B for separating the gaseous product into a condensable liquid product and a non-condensable gaseous product; and
At least one tail gas treatment unit for treating the non-condensable gaseous products to produce olefins, paraffins, and CO 2;
wherein the tail gas of the first Fischer-Tropsch synthesis unit and hydrogen from outside enter a slurry bed reactor B of the second Fischer-Tropsch synthesis unit for reaction.
2. The integrated utilization system for producing hydrocarbons from synthesis gas according to claim 1, wherein: the olefin separation unit includes: an olefin separation unit A is arranged for separating olefin and alkane in the non-condensable gaseous product, and the obtained tail gas enters a second Fischer-Tropsch synthesis unit; and an olefin separation unit B is provided for separating olefins and paraffins in the condensable liquid product.
3. The comprehensive utilization system for producing hydrocarbons from synthesis gas according to claim 1 or 2, wherein: an inner filter A is arranged in the slurry bed reactor A, and an inner filter B is arranged in the slurry bed reactor B, so as to obtain oil products.
4. A comprehensive utilization method for preparing hydrocarbon from synthesis gas is characterized by comprising the following steps: the method comprises the following steps:
1) Introducing synthesis gas comprising CO and H 2 into a slurry bed reactor A of a first Fischer-Tropsch synthesis unit, and carrying out gas-liquid-solid three-phase Fischer-Tropsch synthesis reaction under the action of a catalyst; the reaction temperature is 260-350 ℃ and the reaction pressure is 2-6MPa;
2) The gaseous reaction product in the slurry bed reactor A enters the gas-liquid separation unit A and is separated into condensable liquid product and non-condensable gaseous product therein;
3) The non-condensable gaseous product enters an olefin separation unit A to separate alkane and olefin in tail gas, the separated tail gas enters a slurry bed reactor B of a second Fischer-Tropsch synthesis unit, and the separated tail gas and hydrogen provided by the outside continue to carry out Fischer-Tropsch synthesis reaction; the reaction temperature is 220-280 ℃, and the reaction pressure is 2-4MPa;
4) The gaseous reaction products in the slurry bed reactor B enter the gas-liquid separation unit B and are separated therein into condensable liquid products and non-condensable gaseous products;
5) The non-condensable gaseous products enter a tail gas treatment unit and are treated to obtain alkene, alkane and CO 2.
5. The comprehensive utilization method for preparing hydrocarbon from synthesis gas according to claim 4, wherein: further comprises: and the tail gas obtained after the tail gas treatment unit is treated is taken as recycle gas to enter the slurry bed reactor B for continuously carrying out Fischer-Tropsch synthesis reaction.
6. The comprehensive utilization method for preparing hydrocarbon from synthesis gas according to claim 4 or 5, wherein: the operating parameters of slurry bed reactor a in step 1) were: the reaction temperature is 260-330 ℃, the reaction pressure is 2-6MPa, the air speed of an air tower at the inlet of the reactor is 0.1-0.4 m/s, the airspeed of fresh synthesis gas is 2000-25000 standard square/ton of catalyst/H, the solid content of a slurry bed layer of the reactor is 10-30 wt%, and the volume ratio of the synthesis gas H 2/CO is 1-2.5;
Preferably, the operating parameters of the slurry bed reactor a in step 1) are: the reaction temperature is 280-310 ℃, the reaction pressure is 2.5-4MPa, the air speed of the inlet air tower of the reactor is 0.15-0.3 m/s, the airspeed of fresh synthesis gas is 3000-23000 standard square/ton of catalyst/H, the solid content of the slurry bed layer of the reactor is 10-25 wt%, and the volume ratio of the synthesis gas H 2/CO is 1.5-2.0.
7. The comprehensive utilization method for preparing hydrocarbon from synthesis gas according to claim 4 or 6, wherein: the operating parameters of slurry bed reactor B in step 3) were: the reaction temperature is 220-260 ℃, the reaction pressure is 2-3MPa, the air speed of the inlet air tower of the reactor is 0.1-0.4 m/s, the air speed of fresh synthesis gas is 2000-10000 standard square/ton catalyst/H, the solid content of the slurry bed layer of the reactor is 5-20 wt%, and the volume ratio of the synthesis gas H 2/CO is 1-2.5.
8. The integrated utilization process for producing hydrocarbons from synthesis gas according to any one of claims 4 to 7, wherein: the catalyst used in step 1) is a supported χ -iron carbide composition comprising 55-90 wt.% of a support and 10-45 wt.% of an iron component, wherein the iron component comprises 95-100 mol.% χ -iron carbide and 0-5 mol.% of Fe-containing impurities, based on the total amount of the iron component, which are iron-containing species other than χ -iron carbide; preferably, the composition comprises 60-85 wt% of carrier and 15-40 wt% of iron component, based on the total amount of the iron component, the iron component comprises 97-100mol% of pure χ -iron carbide and 0-3mol% of Fe-containing impurities, the Fe-containing impurities being iron-containing substances other than χ -iron carbide.
9. The integrated utilization process for producing hydrocarbons from synthesis gas according to any one of claims 4 to 7, wherein: the catalyst used in step 1) is a precipitated χ -iron carbide-containing composition comprising 95-100 mole% precipitated χ -iron carbide and 0-5 mole% Fe-containing impurities, which are elemental Fe-containing materials other than χ -iron carbide.
10. The integrated utilization process for producing hydrocarbons from synthesis gas according to any one of claims 4 to 7, wherein: the catalyst used in step 1) is a composition containing χ -iron carbide, the composition comprising 95-100mol% χ -iron carbide and 0-5mol% Fe-containing impurities, the Fe-containing impurities being elemental iron-containing materials other than χ -iron carbide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211239054.4A CN117899761A (en) | 2022-10-11 | 2022-10-11 | Comprehensive utilization system and method for preparing hydrocarbon from synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211239054.4A CN117899761A (en) | 2022-10-11 | 2022-10-11 | Comprehensive utilization system and method for preparing hydrocarbon from synthesis gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117899761A true CN117899761A (en) | 2024-04-19 |
Family
ID=90685686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211239054.4A Pending CN117899761A (en) | 2022-10-11 | 2022-10-11 | Comprehensive utilization system and method for preparing hydrocarbon from synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117899761A (en) |
-
2022
- 2022-10-11 CN CN202211239054.4A patent/CN117899761A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5827903A (en) | Separation of catalyst from Fischer-Tropsch slurry | |
| CN103074097B (en) | Method and system for direct coal liquefaction | |
| JP2003514959A (en) | Method for converting synthesis gas to higher hydrocarbons | |
| CN103170284B (en) | Fischer-Tropsch synthesis system and process of high-temperature and high-pressure slurry bed reactor | |
| US4839030A (en) | Coal liquefaction process utilizing coal/CO2 slurry feedstream | |
| CN101892063A (en) | Fischer-Tropsch synthesis method and system | |
| WO2003087265A1 (en) | Hydrocarbon synthesis process using an alkali promoted iron catalyst | |
| US20070259973A1 (en) | Optimized hydrocarbon synthesis process | |
| EP2643265A1 (en) | Process for improving the hydrogen content of a synthesis gas | |
| CN103396826B (en) | Two-stage series-connected Fischer-Tropsch synthesis system and process thereof | |
| US6903141B2 (en) | Slurry-phase skeletal iron catalyst process for synthesis gas conversion to hydrocarbons | |
| AU689220B2 (en) | Staged hydrocarbon synthesis process | |
| CN113651670B (en) | Method for preparing hanging tetrahydrodicyclopentadiene through hydroisomerization of dicyclopentadiene | |
| CN108530254A (en) | A method of mixing carbon four prepares normal butane | |
| CN106673938A (en) | Method for producing cyclopentene by selective hydrogenation of cyclopentadiene | |
| EP1465850A1 (en) | Water stripping and catalyst/liquid product separation system | |
| US6921778B2 (en) | Process for converting synthesis gas in reactors that are arranged in series | |
| CN213506759U (en) | Enhanced reaction system for direct coal liquefaction | |
| RU2549187C2 (en) | Method of converting synthesis gas using cobalt catalyst at first step and supported ruthenium catalyst at second step | |
| CN117899761A (en) | Comprehensive utilization system and method for preparing hydrocarbon from synthesis gas | |
| EP0128620B1 (en) | Multistage process for the direct liquefaction of coal | |
| CN113651664B (en) | Method for conversion of benzyl alcohol | |
| CN111137859A (en) | Adjustable H for direct cracking preparation and separation of methanol2Process for synthesis gas in ratio to CO | |
| CN112552964A (en) | Micro-interface-based system and process for strengthening coal indirect liquefaction | |
| WO1980001284A1 (en) | Coal liquefaction process with a plurality of feed coals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |