CN103045284A - Fischer-Tropsch synthesis method capable of increasing selectivity for liquid hydrocarbons - Google Patents
Fischer-Tropsch synthesis method capable of increasing selectivity for liquid hydrocarbons Download PDFInfo
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Abstract
The invention relates to a Fischer-Tropsch synthesis method capable of increasing selectivity for liquid hydrocarbons. Two solid bed Fischer-Tropsch synthesis reactors connected in series are arranged. A synthetic gas is subject to a Fischer-Tropsch synthesis reaction in a first reactor, capable of increasing selectivity for liquid hydrocarbons; a mixed gas of an unconverted synthetic gas and a gas produced by the reactor is introduced into a second reactor to react continuously, wherein the diameter of the catalyst particles in the second reactor is smaller than that of the catalyst in the first reactor. Compared with a conventional synthesis reaction carried out by a Fischer-Tropsch synthesis technology, the Fischer-Tropsch synthesis reaction carried out by the method has the advantages of high selectivity for liquid hydrocarbons.
Description
Technical field
The present invention relates to optionally Fischer-Tropsch synthesis method of a kind of raising liquid hydrocarbon.
Background technology
Oil is the grand strategy goods and materials that ensure economic life line of the country and political security.Since the last century the nineties, China's oil consumption constantly increases, and substantially exceeds the rate of growth of the crude production same period, has to rely on the deficiency of providing Domestic Resources by import.China became since the net import of oil state from 1993, and the oil insufficiency of supply-demand enlarges year by year, about 2.5 hundred million tons of crude oil in China imports in 2010, and externally interdependency surpasses 55%.So large-scale petroleum import has increased the degree of dependence of China to foreign oil, and the fluctuation of international petroleum market and variation will directly affect the safety of China's economy and even politics with stable.Therefore, China must walk the road of diversification of resources strategically, greatly develops the petroleum replacing technology, reduces the China's oil risk.
Contain hydrocarbon resource and go out synthetic gas as raw material production so that Sweet natural gas, pitch, coal, biomass etc. are various, again take synthetic gas as raw material by the synthetic liquefied hydrocarbon of producing of Fischer-Tropsch, be a good petroleum replacing technology.Its product oil product mainly is comprised of straight chain hydrocarbon, and after upgrading processing, the product naphtha fraction is the preparing ethylene by steam cracking raw material of high-quality, and the triolefin yield is about 60 % by weight; Sulphur content of diesel fraction is less than 3 μ g/g, and nitrogen content is less than 0.5 μ g/g, and cetane value can satisfy the harshest existing diesel oil standard more than 74; The tail oil cut can be used as the raw material that generates III class or IV lubricant base, has high added value.Along with the raising of people's environmental consciousness, country will make stricter requirement to diesel oil, and the synthetic diesel product of producing of Fischer-Tropsch can be used as the blend component of high hexadecane value, low arene content and qualified diesel product is produced in second-rate diesel oil mediation.
CN 1691978A discloses a kind of parallel reactor operating system.It comprises one or more shared reactant feed lines, two or more single unit operated reactor sections and one or more shared product outfall pipeline.This reactor assembly is particularly suitable for preparing hydrocarbon by synthetic gas under the effect of catalyzer.
US5827902 discloses a kind of multistage slurry attitude bed fischer-tropsch synthetic method, and the method takes the mode of a plurality of paste state bed reactor series connection to operate, and number of reactors is 2-5.
CN101475427A discloses a kind of novel generation fischer-tropsch synthesis process, the method adopts series connection or series and parallel to combine a plurality of fischer-tropsch reactors, gas behind each fischer-tropsch reactor through cooling, separate, after liquid product paraffin, heavy component, light constituent and reaction water taking-up, unreacted tail gas is sent into next fischer-tropsch reactor.This technique is the technique with modularization, easily amplification, one way fecund thing characteristics based on the Fischer-Tropsch synthetic technology of fixed bed.
Summary of the invention
The objective of the invention is on the prior art basis, optionally Fischer-Tropsch synthesis method of a kind of raising liquid hydrocarbon is provided.The method comprises the steps:
(1) synthetic gas enters the first fixed bed Fischer-Tropsch synthesis device, contacts with fischer-tropsch synthetic catalyst I and carries out building-up reactions, produces the first fixed-bed reactor effluent;
(2) first fixed-bed reactor effluents carry out gas-liquid separation, obtain water I, gas I, liquid hydrocarbon I;
(3) the gas I of step (2) gained enters in the second fixed bed Fischer-Tropsch synthesis device, contacts with fischer-tropsch synthetic catalyst II and carries out building-up reactions, produces the second fixed-bed reactor effluent;
(4) second fixed-bed reactor effluents carry out gas-liquid separation, obtain water II, gas II, liquid hydrocarbon II;
(5) the gas II of step (4) gained loops back the first fixed-bed reactor and the reaction of the second fixed-bed reactor sustainable participation;
The equivalent diameter of fischer-tropsch synthetic catalyst II is less than the equivalent diameter of fischer-tropsch synthetic catalyst I in the first fixed-bed reactor in described the second fixed-bed reactor.
Preferred described fischer-tropsch synthetic catalyst II is 1: 1.1～1: 1.8 with the equivalent diameter ratio of fischer-tropsch synthetic catalyst I, and further preferred its equivalent diameter ratio is 1: 1.2～1: 1.6.
The heat-obtaining problem of calandria type fixed bed Fischer-Tropsch synthesis device is one of difficult point of fixed bed Fischer-Tropsch synthetic technology research and development.Finding in inventor's research process how much inert gas content is the key factor that affects unit volume unstripped gas thermal discharge in the synthetic gas, also is to affect the key factor that bed temperature distributes.In addition, catalyst particle size is the important parameter that affects heat diffusion, also is the important factor that affects the building-up reactions effect simultaneously.Therefore, effective synthetic gas density and catalyst particle size in the properly distributed Fischer-Tropsch building-up process of the present invention realize optimum combination with the two, with the maximization liquid hydrocarbon selectivity that realizes that Fischer-Tropsch is synthetic.
In another preferred embodiment, in described the second fixed-bed reactor reaction tube diameter greater than reaction tube diameter in the first fixed-bed reactor.More preferably, in the second fixed-bed reactor in reaction tube diameter and the first fixed-bed reactor ratio of reaction tube diameter be 1.1: 1～1.8: 1, more preferably 1.2: 1～1.6: 1.
The restriction that calandria type fixed bed Fischer-Tropsch synthesis device transmits owing to received heat, the size of its reaction tubes is restricted.For arranging of reaction tubes in the shell and tube reactor, if reaction tubes is too thin, the more reaction tubes although the reactor unit cross-sectional area can be arranged, but the total sectional area of reaction tubes is little, the cumulative volume that means reaction tubes in the unit volume reactor is little, the total filling amount of catalyzer is little, and the output of this reactor will correspondingly reduce so.Therefore, the augmenting response bore is the key factor that improves reactor unit volume output.
In inventor's research process, find, unit gas thermal discharge has directly determined the size of reaction tube diameter, in synthetic gas, allocate in the situation of nitrogen, although augmenting response pipe diameter to a certain extent, but because the existence of rare gas element is actually and has reduced the building-up reactions effect.Therefore, adding rare gas element is not the preferred way that addresses this problem.But, in the Fischer-Tropsch building-up process, can produce a certain amount of methane, and methane to synthesize for Fischer-Tropsch be rare gas element, therefore, method provided by the invention is, utilize the tail gas of reactor the last period as the unstripped gas of rear first stage reactor, both do not add in addition rare gas element, can reduce the thermal discharge of unit volume gas again, and reached the purpose that increases caliber, improves device output.
By between the first fixed-bed reactor and the second fixed-bed reactor, injecting H
2Or CO, the H/C mol ratio of regulating the second fixed-bed reactor entrance.
The operational condition of described the first fixed bed Fischer-Tropsch synthesis device is: 180 ℃～260 ℃ of temperature of reaction, pressure 2.0～5.0MPa, hydrogen carbon monoxide mol ratio 1.6～2.2, air speed 300～1500h
-1
The operational condition of described the second fixed bed Fischer-Tropsch synthesis device is: 180 ℃～260 ℃ of temperature of reaction, pressure 2.0～5.0MPa, hydrogen carbon monoxide mol ratio 1.6～2.2, air speed 300～1500h
-1
The total gas hourly space velocity of described the second fixed-bed reactor is equal to or greater than total gas hourly space velocity of the first fixed-bed reactor.Described total gas hourly space velocity refers to total feeding gas hourly space velocity, has comprised fresh feed gas and circulation gas gas hourly space velocity.Fischer-Tropsch synthesis occurs in synthetic gas in the first reactor, generate a certain amount of methane.Compare with the first reactor, the methane content in the second reactor is higher, and methane can effectively reduce the exothermic heat of reaction of unit volume unstripped gas as the diluent gas of synthetic gas.Therefore in the second reactor, can adopt than gas hourly space velocity higher in the first reactor to operate, thereby improve device output.
The present invention is provided with the fixed bed Fischer-Tropsch synthesis device of two series connection, and synthetic gas in the first reactor Fischer-Tropsch synthesis occurs, and unconverted synthesis gas enters the second reactor with the gas mixture that reacts generation gas and proceeds reaction.Wherein the granules of catalyst diameter in the second reactor is less than the catalyzer diameter in the first reactor.Compare with conventional Fischer-Tropsch synthetic technology, carry out Fischer-Tropsch synthesis by the method, have the high characteristics of building-up reactions liquid hydrocarbon-selective.
Embodiment
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
The preparation process of used fischer-tropsch synthetic catalyst is as follows among the embodiment:
Get aluminum oxide powder (Shandong Aluminum Plant), drip distilled water to just wetting, write down the volume that consumes water, then press Co content 27% and calculate, make the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES steeping fluid.Then extremely just wetting with this solution impregnation aluminum oxide, left standstill 8 hours, with the extrusion agent of orifice plate diameter 1.4mm with catalyst extruded forming, then in 120 ℃ of dryings 4 hours, 450 ℃ of roastings made catalyst A in 4 hours in muffle furnace, finished catalyst A equivalent diameter 1.1mm.
Get aluminum oxide powder (Shandong Aluminum Plant), drip distilled water to just wetting, write down the volume that consumes water, then press Co content 27% and calculate, make the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES steeping fluid.Then extremely just wetting with this solution impregnation aluminum oxide, left standstill 8 hours, with the extrusion agent of orifice plate diameter 1.8mm with catalyst extruded forming, then in 120 ℃ of dryings 4 hours, 450 ℃ of roastings made catalyst B in 4 hours in muffle furnace, finished catalyst B equivalent diameter 1.4mm.
Comparative Examples 1
Getting the 100mL catalyst A is that the fixed bed Fischer-Tropsch synthetic test equipment of 26mm is tested in reaction tube diameter.Reactor operating condition is: 210 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h-1.The building-up reactions effect sees Table 1.
Comparative Examples 2
Getting the 100mL catalyst A is that the fixed bed Fischer-Tropsch synthetic test equipment of 32mm is tested in reaction tube diameter, plan will be 2.0 in 210 ℃ of average reaction temperature, pressure 3.0MPa, reactor inlet H/C mol ratio, test under the operational condition of air speed 500h-1, but beds overtemperature when temperature rises to 203 ℃, test can't be carried out.
Comparative Examples 3
Getting the 100mL catalyst B is that the fixed bed Fischer-Tropsch synthetic test equipment of 26mm is tested in reaction tube diameter.Reactor operating condition is: 210 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h-1.The building-up reactions effect sees Table 1.
Comparative Examples 4
Getting the 100mL catalyst B is that the fixed bed Fischer-Tropsch synthetic test equipment of 32mm is tested in reaction tube diameter.Reactor operating condition is: 210 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h-1.The building-up reactions effect sees Table 1.
Comparative Examples 5
Getting the 100mL catalyst A is that the fixed bed Fischer-Tropsch synthetic test equipment of 32mm is tested in reaction tube diameter, allocate the methane of 5 volume % in synthetic gas into, reactor operating condition is: 210 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, fresh synthesis gas air speed 500h-1.The building-up reactions effect sees Table 1.
Table 1
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | |
| Catalyzer | A | A | B | B | A |
| Tube inner diameter, mm | 26 | 32 | 26 | 32 | 32 |
| The CO transformation efficiency, mol% | 89.32 | Overtemperature | 83.65 | 82.82 | 87.39 |
| CH 4Selectivity, mol% | 6.32 | Overtemperature | 8.21 | 9.96 | 7.68 |
| The C5+ selectivity, mol% | 89.20 | Overtemperature | 84.67 | 81.23 | 86.61 |
Can be found out that by Comparative Examples 1～Comparative Examples 4 the reaction effect difference of the catalyzer of different equivalent diameters in the different diameter reaction tubes is very large, this mainly is by due to exothermic heat of reaction and the heat transfer process difference.The equivalent diameter of granules of catalyst is less, and the building-up reactions effect is better; Reaction tube diameter is less, the building-up reactions effect is better.
The size of reaction tube diameter has directly determined the loadings of catalyst in reactor, has also determined the complexity of catalyst loading process, especially when the large-scale industry device is implemented, and the content that emphasis was considered when reaction tube diameter was the device design.Illustrate, adopt the catalyzer of equal volume to carry out Fischer-Tropsch synthesis, in the identical situation of reaction tubes height, adopt the reaction tubes of internal diameter 26mm than the reaction tubes that adopts 32mm 51% reaction tubes to be set more, want how consuming time about 50% when this just means catalyst loading, can be found out that by Comparative Examples 2 reaction tube diameter causes overtemperature too greatly easily, therefore avoiding under the prerequisite of overtemperature, select major diameter reaction pipe is one of target of device design pursuit as far as possible.
Although catalyst particle has the excellent characteristics of building-up reactions effect, in major diameter reaction pipe, because heat can not in time spread out of, can cause the beds overtemperature, Comparative Examples 2 has just illustrated this problem.On the basis of Comparative Examples 2, allocate the methane of 5 volume % in the synthetic gas into and test (Comparative Examples 5), can find out overtemperature does not occur in the process of the test, test smooth.This is because methane belongs to rare gas element in the Fischer-Tropsch synthesis process, and the existence of methane effectively reduces effecting reaction gas concentration in the unit volume unstripped gas, reduced the thermal discharge of unit volume gas.
In order to overcome the problems referred to above, technical scheme of the present invention is, when the Large Diameter Pipeline reactor carries out Fischer-Tropsch synthesis, adopt two reactors of series connection, filling major diameter catalyzer can effectively be avoided overtemperature in first reactor, filling minor diameter catalyzer had both improved the liquid hydrocarbon selectivity in second reactor, again because the existence of the methane that produces in first reactor can be avoided the overtemperature of catalyst particle in major diameter reaction pipe.
Embodiment 1
Getting the 60mL catalyst B is seated in the reaction tubes that first diameter is 32mm, getting the 40mL catalyst A, to be seated in second diameter be in the reaction tubes of 32mm, behind first reactor Separate System of Water-jet is set, isolated gas enters second reactor and proceeds to participate in reaction.
The operational condition of the first reactor and the second reactor is: 210 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, fresh synthesis gas air speed 500h
-1The building-up reactions effect sees Table 2.
Table 2
| Embodiment 1 | |
| The CO transformation efficiency, mol% | 85.89 |
| CH 4Selectivity, mol% | 8.02 |
| The C5+ selectivity, mol% | 84.77 |
By embodiment 1 result as seen, adopt the method for the invention in the reaction tubes of tube inner diameter 32mm, to carry out Fischer-Tropsch synthesis, overheating problem has not both occured, obtained again preferably reaction effect.
Embodiment 2
Getting the 70mL catalyst B is seated in the reaction tubes that first diameter is 32mm, getting the 30mL catalyst A, to be seated in second diameter be in the reaction tubes of 38mm, behind first reactor Separate System of Water-jet is set, isolated gas enters second reactor and proceeds to participate in reaction.
The operational condition of the first reactor and the second reactor is: 212 ℃ of medial temperatures, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, fresh synthesis gas air speed 550h
-1The building-up reactions effect sees Table 2.
Table 3
| Embodiment 2 | |
| The CO transformation efficiency, mol% | 86.29 |
| CH 4Selectivity, mol% | 8.23 |
| The C5+ selectivity, mol% | 84.16 |
By embodiment 2 results as seen, adopt the method for the invention to carry out Fischer-Tropsch synthesis, overheating problem has not both occured, obtained again preferably reaction effect.
Claims (9)
1. one kind is improved optionally Fischer-Tropsch synthesis method of liquid hydrocarbon, comprises the steps:
(1) synthetic gas enters the first fixed bed Fischer-Tropsch synthesis device, contacts with fischer-tropsch synthetic catalyst I and carries out building-up reactions, produces the first fixed-bed reactor effluent;
(2) first fixed-bed reactor effluents carry out gas-liquid separation, obtain water I, gas I, liquid hydrocarbon I;
(3) the gas I of step (2) gained enters in the second fixed bed Fischer-Tropsch synthesis device, contacts with fischer-tropsch synthetic catalyst II and carries out building-up reactions, produces the second fixed-bed reactor effluent;
(4) second fixed-bed reactor effluents carry out gas-liquid separation, obtain water II, gas II, liquid hydrocarbon II;
(5) the gas II of step (4) gained loops back the first fixed-bed reactor and the reaction of the second fixed-bed reactor sustainable participation;
The equivalent diameter of fischer-tropsch synthetic catalyst II is less than the equivalent diameter of fischer-tropsch synthetic catalyst I in the first fixed-bed reactor in described the second fixed-bed reactor.
2. in accordance with the method for claim 1, it is characterized in that described fischer-tropsch synthetic catalyst II is 1: 1.1～1: 1.8 with the equivalent diameter ratio of fischer-tropsch synthetic catalyst I.
3. in accordance with the method for claim 1, it is characterized in that described fischer-tropsch synthetic catalyst II is 1: 1.2～1: 1.6 with the equivalent diameter ratio of fischer-tropsch synthetic catalyst I.
4. in accordance with the method for claim 1, it is characterized in that, by between the first fixed-bed reactor and the second fixed-bed reactor, injecting H
2Or CO, the H/C mol ratio of regulating the second fixed-bed reactor entrance.
5. in accordance with the method for claim 1, it is characterized in that reaction tube diameter is greater than reaction tube diameter in the first fixed-bed reactor in described the second fixed-bed reactor.
6. in accordance with the method for claim 5, it is characterized in that, in the second fixed-bed reactor in reaction tube diameter and the first fixed-bed reactor ratio of reaction tube diameter be 1.1: 1～1.8: 1.
7. in accordance with the method for claim 6, it is characterized in that, in the second fixed-bed reactor in reaction tube diameter and the first fixed-bed reactor ratio of reaction tube diameter be 1.2: 1～1.6: 1.
8. in accordance with the method for claim 1, it is characterized in that the operational condition of described the first fixed bed Fischer-Tropsch synthesis device is: 180 ℃～260 ℃ of temperature of reaction, pressure 2.0～5.0MPa, hydrogen carbon monoxide mol ratio 1.6～2.2, air speed 300～1500h
-1
The operational condition of described the second fixed bed Fischer-Tropsch synthesis device is: 180 ℃～260 ℃ of temperature of reaction, pressure 2.0～5.0MPa, hydrogen carbon monoxide mol ratio 1.6～2.2, air speed 300～1500h
-1
9. according to claim 1 or 8 described methods, it is characterized in that the total gas hourly space velocity of described the second fixed-bed reactor is equal to or greater than total gas hourly space velocity of the first fixed-bed reactor.
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