CN103007836B - Method for improving yield of Fischer-Tropsch synthesis device - Google Patents
Method for improving yield of Fischer-Tropsch synthesis device Download PDFInfo
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Abstract
The invention discloses a method for improving a yield of a Fischer-Tropsch synthesis device. The method is characterized in that two Fischer-Tropsch synthesis reactors connected in series are adopted; synthetic gas undergoes a Fischer-Tropsch synthesis reaction in a first reactor; and mixed gas of unconverted synthetic gas and reaction product gas is fed into a second reactor and undergoes a reaction, wherein the diameter of a reaction pipe in the second reactor is greater than the diameter of a reaction pipe in the first reactor. Compared with the conventional Fischer-Tropsch synthesis technology, the method improves a synthetic oil yield of a unit volume of a reactor.
Description
Technical field
The present invention relates to a kind of Fischer-Tropsch synthesis method, more particularly, is a kind of method improving fixed bed F-T synthesis device output.
Background technology
Oil is the grand strategy goods and materials ensureing economic life line of the country and political security.Since last century the nineties, China's oil consumption constantly increases, and substantially exceeds the growth rate of the crude oil production same period, has to rely on the deficiency providing Domestic Resources by import.Since 1993 Nian Qi China become net import of oil state, oil insufficiency of supply-demand expands year by year, and crude oil in China import in 2010 about 2.5 hundred million tons, external dependence degree is more than 55%.So large-scale petroleum import, adds the degree of dependence of China to foreign oil, and the fluctuation of international petroleum market and change will directly affect the safety of China's economy and even politics and stablize.Therefore, China must walk the road of diversification of resources strategically, greatly develops petroleum replacing technology, reduces China's oil risk.
With natural gas, pitch, coal, living beings etc. various containing hydrocarbon resource for synthesis gas produced by raw material, then being that raw material produces liquefied hydrocarbon by F-T synthesis with synthesis gas, is a good petroleum replacing technology.Its product oil product forms primarily of straight-chain hydrocarbons, and after upgrading processing, product naphtha cut is the preparing ethylene by steam cracking raw material of high-quality, and 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 number, more than 74, can meet the harshest existing diesel oil standard; Tail oil fraction can be used as the raw material generating III class or IV lube base oil, has high added value.Along with the raising of people's environmental consciousness, country makes stricter requirement by diesel oil, and the diesel product that F-T synthesis is produced can be used as high cetane number, the blend component of low arene content and second-rate diesel oil blending and produces qualified diesel product.
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 discharge pipe line.This reactor assembly to be particularly suitable under the effect of catalyst by synthesis gas to prepare hydrocarbon.
US5827902 discloses a kind of multistage slurry bed system Fiscber-Tropscb synthesis method, and the mode that the method takes multiple paste state bed reactor to connect operates, and number of reactors is 2-5.
CN101475427A discloses a kind of novel generation fischer-tropsch synthesis process, multiple fischer-tropsch reactor adopts series connection or series and parallel to combine by the method, gas after each fischer-tropsch reactor through cooling, be separated, after liquid product paraffin, heavy component, light component and reaction water being taken out, unreacted tail gas sends into next fischer-tropsch reactor.This technique, based on the F-T synthesis technology of fixed bed, is the technique with modularization, easily amplification, one way fecund thing feature.
Prior art unistage type flow process as shown in Figure 1, eliminate boiler system, valve, instrument etc., but this does not affect the understanding of those skilled in the art to this flow process in figure.Synthesis gas enters reactor R1 by pipeline 1, Fischer-Tropsch synthesis is carried out under the effect of catalyst, reactor effluent enters high pressure hot separator V1 through pipeline 2, gas-liquid separation is carried out in V1, gained gas fraction enters cold high pressure separator V2 through pipeline 3, and liquid part enters thermal low-pressure separators V4 through pipeline 6.Enter logistics further gas-liquid separation in this separator of cold high pressure separator V2, gained liquid part enters cold low separator V3 through pipeline 4, and gained gas fraction participates in reaction through pipeline 8 further by returning R1 through pipeline 9 after compressor C1 supercharging.By obtaining synthesis light oil and water bottom cold low separator V3, after pipeline 5 is extracted out, with separatory funnel by water be separated.Bottom thermal low-pressure separators V4, obtain synthesis of heavy oil, and discharge through pipeline 7.Reactor R1 can be replaced by the reactor of different-diameter flexibly,
The flow process of raising F-T synthesis device throughput method (two sections of tandems) provided by the invention as shown in Figure 2, eliminate boiler system, valve, instrument etc., but this does not affect the understanding of those skilled in the art to this flow process in figure.Synthesis gas enters reactor R1 by pipeline 1, Fischer-Tropsch synthesis is carried out under the effect of catalyst, reactor effluent enters high pressure hot separator V1 through pipeline 2, gas-liquid separation is carried out in high pressure hot separator V1, gained gas fraction enters cold high pressure separator V2 through pipeline 3, and gained liquid part enters thermal low-pressure separators V4 through pipeline 6.Enter logistics further gas-liquid separation in this separator of cold high pressure separator V2, gained liquid part enters cold low separator V3 through pipeline 4, and gained gas fraction enters reactor R2 through pipeline 8.By obtaining synthesis light oil and water bottom cold low separator V3, after pipeline 5 is extracted out, be separated with oil with separatory funnel Jiang Shui.Bottom thermal low-pressure separators V4, obtain synthesis of heavy oil, and discharge through pipeline 7.
The gas entering R2 carries out Fischer-Tropsch synthesis under the effect of catalyst, reactor R2 effluent enters high pressure hot separator V5 through pipeline 9, gas-liquid separation is carried out in high pressure hot separator V5, gained gas fraction enters cold high pressure separator V6 through pipeline 10, and gained liquid part enters thermal low-pressure separators V8 through pipeline 13.Enter logistics further gas-liquid separation in this separator of cold high pressure separator V6, the liquid part obtained enters cold low separator V7 through pipeline 11, and the gas fraction obtained participates in reaction through pipeline 16 and pipeline 17 Returning reactor R1 and reactor R2 through pipeline 15 respectively further by after compressor C1 supercharging.Obtain synthesis light oil and water bottom cold low separator V7, after pipeline 12 is extracted out, be separated with oil with separatory funnel Jiang Shui.Obtain synthesis of heavy oil bottom thermal low-pressure separators V8 to extract out through pipeline 14.Reactor R1 and reactor R2 can be replaced by the reactor of different-diameter flexibly.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Summary of the invention
The object of the invention is on prior art basis, a kind of method improving F-T synthesis device output is provided.This comprises the steps:
(1) synthesis gas enters the first fixed bed Fischer-Tropsch synthesis device and carries out synthetic reaction, produces the first fixed bed reactors effluent;
(2) first fixed bed reactors 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 and carries out synthetic reaction, produces the second fixed bed reactors effluent;
(4) second fixed bed reactors 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 reactors and the second fixed bed reactors continuation participation reaction;
In the second described fixed bed reactors, reaction tube diameter is greater than reaction tube diameter in the first fixed bed reactors.
The restriction that calandria type fixed bed Fischer-Tropsch synthesis device transmits due to received heat, the size of its reaction tube is restricted.For the arrangement of reaction tube in shell and tube reactor, if reaction tube is too thin, the more reaction tube although reactor unit cross-sectional area can be arranged, but the total sectional area of reaction tube is little, mean that the cumulative volume of reaction tube in unit volume reactor is little, the total filling amount of catalyst is little, so the output of this reactor will correspondingly reduce.Therefore, augmenting response bore is the key factor improving reactor unit volume output.
Find in the research process of inventor, unit-gas thermal discharge directly determines the size of reaction tube diameter, when allocating nitrogen in synthesis gas, although can augmenting response pipe diameter to a certain extent, but due to the existence of inert gas, be actually and reduce synthetic reaction effect.Therefore, adding inert gas is not the preferred way solving this problem.But, in Fischer-Tropsch synthesis, a certain amount of methane can be produced, and methane is inert gas for F-T synthesis, 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 inert gas in addition, the thermal discharge of unit volume gas can be reduced again, and reach the object increasing caliber, improve device output.
By injecting H between the first fixed bed reactors and the second fixed bed reactors
2or CO, regulate the H/C mol ratio of the second fixed bed reactors entrance.
In described second fixed bed reactors, in reaction tube diameter and the first fixed bed reactors, the ratio of reaction tube diameter is 1.1: 1 ~ 1.8: 1, and preferred ratio is 1.2: 1 ~ 1.6: 1.
The operating condition of described first fixed bed Fischer-Tropsch synthesis device is: reaction temperature 180 DEG C ~ 260 DEG C, pressure 2.0 ~ 5.0MPa, hydrogen carbon monoxide mol ratio 1.6 ~ 2.2, air speed 300 ~ 1500h
-1.
The operating condition of described second fixed bed Fischer-Tropsch synthesis device is: reaction temperature 180 DEG C ~ 260 DEG C, pressure 2.0 ~ 5.0MPa, hydrogen carbon monoxide mol ratio 1.6 ~ 2.2, air speed 300 ~ 1500h
-1.
The present invention is provided with the fixed bed Fischer-Tropsch synthesis devices of two series connection, and synthesis gas, in the first reactor, Fischer-Tropsch synthesis occurs, and the gaseous mixture that unconverted synthesis gas and reaction generate gas enters the second reactor and proceeds to react.Wherein in the second reactor, reaction tube diameter is greater than the reaction tube diameter of the first reactor.Compared with conventional F-T synthesis technology, invention increases the artificial oil output of unit volume reactor.
Accompanying drawing explanation
Fig. 1 is unistage type Fischer-Tropsch synthesis method schematic flow sheet in prior art.
Fig. 2 is the schematic flow sheet of raising F-T synthesis device throughput method provided by the invention.
Detailed description of the invention
Below by accompanying drawing to method of the present invention, be further described, but not thereby limiting the invention.
Fischer-tropsch synthetic catalyst used in embodiment is the RFT-2 fixed bed FischerTropsch synthesis catalyst that China Petrochemical Industry's catalyst Chang Ling branch company produces.
In comparative example and embodiment, Fischer-Tropsch synthesis device used is drum steam heat-obtaining formula single tube fixed bed reactors, has unistage type and two sections of tandems, two kinds of flow processs.Each reactor center is the Thermal couple casing pipe of diameter 6mm, and for monitoring bed temperature, each catalyst reactor bed height is 1.8m.
Comparative example 1
Test with the reaction system of unistage type shown in Fig. 1, testing reactor used R1 internal diameter is 32mm, and loaded catalyst is 1400mL, bed height 1.8m.Reactor operating condition is: mean temperature 200 ~ 215 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h-1, recycle ratio 11.5.Synthetic reaction effect and oil production are in table 1.
Table 1
| Reaction temperature, DEG C | 200 | 205 | 210 | 215 |
| CO conversion ratio, mol% | 48.47 | 69.96 | 83.96 | 93.39 |
| CH 4Selective, mol% | 6.53 | 7.05 | 7.53 | 8.06 |
| C 5+Selective, mol% | 87.35 | 86.72 | 86.35 | 86.09 |
| Oil+wax output, g/h | 91.3 | 131.8 | 158.1 | 175.9 |
Comparative example 2
Test with the reaction system of unistage type shown in Fig. 1, testing reactor used R1 internal diameter is 36mm, and loaded catalyst is 1780mL, bed height 1.8m.Reactor operating condition is: mean temperature 200 ~ 205 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h-1, recycle ratio 11.5.Synthetic reaction effect and oil production are in table 2.This test gets group reaction data 200 DEG C time, but in 205 DEG C of temperature-rise periods, beds overtemperature, test cannot proceed.
Table 2
| Reaction temperature, DEG C | 200 | 205 |
| CO conversion ratio, mol% | 48.91 | Overtemperature |
| CH 4Selective, mol% | 6.69 | Overtemperature |
| C 5+Selective, mol% | 87.06 | Overtemperature |
| Oil+wax output, g/h | 113.5 | Overtemperature |
Comparative example 3
Test with the reaction system of two-part shown in Fig. 2, test reactor used R1 and R2 internal diameter and be 32mm, two catalyst reactor loadings are 1400mL, and total catalyst loading amount 2800mL, bed height is 1.8m.Reactor R1 operating condition is: mean temperature 200 ~ 215 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h
-1, recycle ratio 11.5.Reactor R2 operating condition is: mean temperature 200 ~ 215 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, recycle ratio 11.5.Synthetic reaction effect and oil production are in table 3.
Table 3
| One anti-/ bis-anti-temperature, DEG C | 200/200 | 205/205 | 210/210 | 215/215 |
| CO conversion ratio, mol% | 49.56 | 71.06 | 84.62 | 94.06 |
| CH 4Selective, mol% | 6.25 | 6.91 | 7.12 | 7.76 |
| C 5+Selective, mol% | 87.96 | 87.26 | 87.01 | 86.83 |
| Oil+wax output, g/h | 189.2 | 271.3 | 323.1 | 359.1 |
Comparative example 4
Test with the reaction system of two-part shown in Fig. 2, test reactor used R1 and R2 internal diameter and be 36mm, two catalyst reactor loadings are 1780mL, and total catalyst loading amount 3560mL, bed height is 1.8m.Reactor R1 operating condition is: mean temperature 200 ~ 205 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h
-1, recycle ratio 11.5.Reactor R2 operating condition is: mean temperature 200 ~ 205 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, recycle ratio 11.5.Synthetic reaction effect and oil production are in table 4.This test gets group reaction data 200 DEG C time, but in 205 DEG C of temperature-rise periods, beds overtemperature, test cannot proceed.
Table 4
| One anti-/ bis-anti-temperature, DEG C | 200/200 | 205/205 |
| CO conversion ratio, mol% | 49.31 | Overtemperature |
| CH 4Selective, mol% | 6.35 | Overtemperature |
| C 5+Selective, mol% | 87.26 | Overtemperature |
| Oil+wax output, g/h | 235.0 | Overtemperature |
Embodiment 1
Test with the reaction system of two-part shown in Fig. 2, testing reactor used R1 internal diameter is 32mm, reactor R2 internal diameter is 36mm, in R1, loaded catalyst is 1400mL, in R2, loaded catalyst is 1780mL, total catalyst loading amount 3180mL, two reactor catalyst bed heights are 1.8m.Reactor R1 operating condition is: mean temperature 200 ~ 215 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, air speed 500h
-1, recycle ratio 11.5.Reactor R2 operating condition is: mean temperature 200 ~ 215 DEG C, pressure 3.0MPa, reactor inlet H/C mol ratio are 2.0, recycle ratio 11.5.Synthetic reaction effect and oil production are in table 5.
Table 5
| One anti-/ bis-anti-temperature, DEG C | 200/200 | 205/205 | 210/210 | 215/215 |
| CO conversion ratio, mol% | 49.38 | 71.95 | 85.06 | 94.29 |
| CH 4Selective, mol% | 6.32 | 7.03 | 7.29 | 7.86 |
| C 5+Selective, mol% | 87.61 | 87.02 | 86.64 | 86.39 |
| Oil+wax output, g/h | 212.0 | 312.0 | 367.4 | 407.3 |
As can be seen from the response data in comparative example 1 and comparative example 2 when 200 DEG C, under identical process conditions, adopt Large Diameter Pipeline reactor can obtain higher oil production.But Large Diameter Pipeline reactor there will be overtemperature when high-temperature operation, namely cannot at high temperature operate.
As can be seen from the response data of comparative example 1 and comparative example 3, under identical process conditions, two stage process flow process has better reaction effect.Compared with unistage type flow process, under close conversion ratio, two-part flow process has lower CH
4selective and higher C
5+selective, more than the oil production of the two-part flow process twice higher than unistage type flow process.Illustrate that two-part flow process can obtain higher device output.
As can be seen from comparative example 3 and comparative example 4, adopt two stage process flow process, the overtemperatute of major diameter reactor cannot be solved.
As can be seen from adopting the embodiment 1 of the method for the invention, second segment reactor adopts Large Diameter Pipeline reactor at a higher temperature still can stable operation, overtemperature does not occur.Under the operating condition of 215 DEG C, adopt the device oil production of the method for the invention higher than comparative example 3 by 13.4%.
These results suggest that the output adopting the method for the invention significantly can improve F-T synthesis device.
Claims (5)
1. improve a method for F-T synthesis device output, comprise the steps:
(1) synthesis gas enters the first fixed bed Fischer-Tropsch synthesis device and carries out synthetic reaction, produces the first fixed bed reactors effluent;
(2) first fixed bed reactors 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 and carries out synthetic reaction, produces the second fixed bed reactors effluent;
(4) second fixed bed reactors 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 reactors and the second fixed bed reactors continuation participation reaction;
In the second described fixed bed reactors, reaction tube diameter is greater than reaction tube diameter in the first fixed bed reactors, and in the second fixed bed reactors, in reaction tube diameter and the first fixed bed reactors, the ratio of reaction tube diameter is 1.1: 1 ~ 1.8: 1.
2. in accordance with the method for claim 1, it is characterized in that, by injecting H between the first fixed bed reactors and the second fixed bed reactors
2or CO, regulate the H/C mol ratio of the second fixed bed reactors entrance.
3. in accordance with the method for claim 1, it is characterized in that, in the second fixed bed reactors, in reaction tube diameter and the first fixed bed reactors, the ratio of reaction tube diameter is 1.2: 1 ~ 1.6: 1.
4. in accordance with the method for claim 1, it is characterized in that, the operating condition of described first fixed bed Fischer-Tropsch synthesis device is: reaction temperature 180 DEG C ~ 260 DEG C, pressure 2.0 ~ 5.0MPa, hydrogen carbon monoxide mol ratio 1.6 ~ 2.2, air speed 300 ~ 1500h
-1.
5. in accordance with the method for claim 4, it is characterized in that, the operating condition of described second fixed bed Fischer-Tropsch synthesis device is: reaction temperature 180 DEG C ~ 260 DEG C, pressure 2.0 ~ 5.0MPa, hydrogen carbon monoxide mol ratio 1.6 ~ 2.2, air speed 300 ~ 1500h
-1.
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