CN103007835B - Fischer-Tropsch synthesis device starting method - Google Patents
Fischer-Tropsch synthesis device starting method Download PDFInfo
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- CN103007835B CN103007835B CN201110284454.2A CN201110284454A CN103007835B CN 103007835 B CN103007835 B CN 103007835B CN 201110284454 A CN201110284454 A CN 201110284454A CN 103007835 B CN103007835 B CN 103007835B
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Abstract
The invention discloses a Fischer-Tropsch synthesis device starting method. The Fischer-Tropsch synthesis device starting method comprises the following step that 1, a Fischer-Tropsch synthesis catalyst is reduced by reduction gas at a temperature of 300 to 600 DEG C; 2, a Fischer-Tropsch synthesis reaction process is carried out under the condition of an axial temperature difference delta T1 of a catalyst bed; 3, a Fischer-Tropsch synthesis reaction process is carried out under the condition of an axial temperature difference delta T2 of the catalyst bed; and 4, a Fischer-Tropsch synthesis reaction process is carried out under the condition of an axial temperature difference delta T3 of the catalyst bed so that a liquid hydrocarbon is produced, wherein the axial temperature difference delta T1 is more than 0DEG C and less than 1/2 of the axial temperature difference delta T2; and the axial temperature difference delta T2 is more than 1/3 the axial temperature difference delta T3 and less than 2/3 of the axial temperature difference delta T3. The Fischer-Tropsch synthesis device starting method can solve the problem that in Fischer-Tropsch synthesis device starting, a temperature is over the standard temperature easily, and can improve starting smoothness.
Description
Technical field
The present invention relates to a kind of start-up method of F-T synthesis device.
Background technology
F-T synthesis is a strong exothermal reaction, goes into operation the initial stage at device, because catalyst initial activity is higher, be very easy to cause beds to occur hot localised points, if worsening appears in focus, beds overtemperature will be caused, cause catalyst performance to decline and even scrap.Therefore, steadily going into operation of F-T synthesis device is realized extremely important for the high-efficiency operation of device.
CN1167650C discloses a kind of production method of being synthesized hydrocarbon by synthesis gas.The method utilizes the dilution synthesis gas Synthin under the effect of catalyst containing nitrogen.This method by adding the reduction of nitrogen realization response substrate concentration in synthesis gas, thus reduces the thermal discharge of unit volume unstripped gas, realizes the effective control to bed temperature.
US20050154069A1 discloses a kind of Fischer-Tropsch synthesis carried out under nitrogen-containing pollutant.Fischer-Tropsch synthesis of the present invention is carry out in the synthesis gas of 100ppb ~ 3ppm in nitrogen-containing pollutant concentration.Control catalyst activity by introducing nitrogen-containing pollutant, control CO conversion ratio is at least 50% ~ 65% under the non-intoxication conditions of catalyst, and then improves reaction temperature CO conversion ratio is increased to normal level.The method makes catalyst member poisoning by introducing pollutant, thus suppresses catalyst activity, controls exothermic heat of reaction amount.
Although said method alleviates to some extent the problem by the excessive bed temperature skewness brought of thermal discharge, these methods all introduce the material except synthesis gas, bring greater inconvenience in device actual motion.
Summary of the invention
The object of the invention is on prior art basis, provide a kind of F-T synthesis device start-up method, to solve the problem that the F-T synthesis device initial stage of going into operation exists overtemperature risk, improve device and to go into operation initial stage run stability.
The start-up method provided comprises the steps:
(1) fischer-tropsch synthetic catalyst reduces in reducibility gas;
(2) at beds axial temperature difference be Δ T1 operating condition under carry out Fischer-Tropsch synthesis 4 ~ 48h;
(3) at beds axial temperature difference be Δ T2 operating condition under carry out Fischer-Tropsch synthesis 4 ~ 48h;
(4) at beds axial temperature difference be Δ T3 operating condition under carry out Fischer-Tropsch synthesis, to produce liquid hydrocarbon.
The relation of described Δ T1, Δ T2, Δ T3 meets following condition: 0 DEG C of < Δ T1 < (1/2) Δ T2; (1/3) Δ T3 < Δ T2 < (2/3) Δ T3.
Described Δ T1 is 2 DEG C ~ 5 DEG C.
Described F-T synthesis device is fixed bed F-T synthesis device.
Described fischer-tropsch synthetic catalyst is Co based Fischer-Tropsch synthesis catalyst.
The described catalyst reduction condition of step (1) is: temperature 300 ~ 600 DEG C, pressure 0.1 ~ 2.0MPa, gas hourly space velocity 300 ~ 3000h
-1.
Step (1) described reducibility gas is the mist of hydrogen or hydrogen and nitrogen, and in mist, the volume fraction of hydrogen is 2% ~ 99%.
Step (2) ~ described Fischer-Tropsch synthesis condition of step (4) is: temperature 170 ~ 280 DEG C, pressure 1.0 ~ 5.0MPa, fresh synthesis gas air speed 300 ~ 3000h
-1, fresh synthesis gas H:Cmoleratio 0.5 ~ 3.0, gas recycle ratio 1 ~ 10.
The present invention, by controlling the beds temperature difference of different phase run, makes it tide over the high activity stage safely, steadily going into operation of implement device.Significantly reduce F-T synthesis device to go into operation the overtemperature risk at initial stage, improve device and to go into operation initial stage run stability.In addition, the present invention, when implementing, does not need any material outside additional synthesis gas, simple and practical in operation.
Accompanying drawing explanation
Fig. 1 is thermocouple distribution map in fixed bed Fischer-Tropsch synthesis device.
Detailed description of the invention
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
In embodiment, experimental rig is fixed bed F-T synthesis device, drum heat-obtaining mode is adopted to move heat, catalyst in reactor loading amount 800mL, catalyst bed layer height 1200mm, reaction tube center arranges Thermal couple casing pipe, in-built 6 thermocouples of sleeve pipe carry out the monitoring of bed axial temperature, and thermocouple distribution is shown in shown in accompanying drawing 1.
In embodiment, catalyst is cobalt-based fixed bed FischerTropsch synthesis catalyst RFT-2, is produced by China Petrochemical Industry's catalyst Chang Ling branch company.
Embodiment 1
After cobalt-based fixed bed FischerTropsch synthesis catalyst is loaded reactor, first reduce to catalyst in pure hydrogen atmosphere, reducing condition is: temperature 400 DEG C, pressure 0.5MPa, gas space velocity 500h
-1, recovery time 24h.
Catalyst after reduction is cooled to 150 DEG C in hydrogen atmosphere, introduces synthesis gas (gas space velocity 500h in reactor
-1hydrogen/carbon monoxide mole ratios 2.0), and system pressure is risen to 2.5MPa, rise to after required value until pressure, start recycle compressor and set up gas circulation (controlled circulation ratio is 8.0), and with the heating rate of 2 DEG C/h, bed mean temperature is risen to 190 DEG C, and at 190 DEG C constant temperature 24h, this, bed temperature distribution was in table 1 in stage.
Catalyst after constant temperature 24h, continues, with the heating rate of 1 DEG C/h, bed mean temperature is risen to 200 DEG C at 190 DEG C, and at 200 DEG C constant temperature 24h, this, bed temperature distribution was in table 1 in stage.
Catalyst after constant temperature 24h, continues, with the heating rate of 1 DEG C/h, bed mean temperature is risen to 210 DEG C at 200 DEG C, carries out Fischer-Tropsch synthesis at such a temperature and produces liquid hydrocarbon, and this stage bed temperature distribution is in table 1, and Fischer-Tropsch synthesis effect is in table 2.
The present embodiment Δ T1=1.9 DEG C, Δ T2=4.0 DEG C, Δ T3=6.1 DEG C, meet:
0℃＜ΔT1＜(1/2)ΔT2；(1/3)ΔT3＜ΔT2＜(2/3)ΔT3。Illustrate and adopt the method for the invention can realize steadily going into operation of F-T synthesis device.
Table 1 bed temperature distributes
| Bed mean temperature/DEG C | 190 | 200 | 210 |
| Thermocouple 1 | 189.2 | 198.1 | 206.6 |
| Thermocouple 2 | 189.8 | 199.7 | 208.9 |
| Thermocouple 3 | 191.1 | 202.1 | 212.7 |
| Thermocouple 4 | 190.2 | 200.9 | 210.5 |
| Thermocouple 5 | 189.6 | 200.2 | 209.2 |
| Thermocouple 6 | 189.3 | 199.3 | 208.3 |
| The bed temperature difference/DEG C | 1.9 | 4.0 | 6.1 |
Table 2 Fischer-Tropsch synthesis effect
| Reaction condition | |
| Mean temperature/DEG C | 210 |
| The bed temperature difference/DEG C | 6.1 |
| Hydrogen-carbon ratio | 2.0 |
| Recycle ratio | 8.0 |
| Pressure/MPa | 2.5 |
| Air speed/h -1 | 500 |
| Reaction effect | |
| CO conversion ratio/mol% | 88.92 |
| CH 4Selective/mol% | 8.67 |
| C 5+Selective/mol% | 86.72 |
Embodiment 2
After cobalt-based fixed bed FischerTropsch synthesis catalyst is loaded reactor, first reduce to catalyst in pure hydrogen atmosphere, reducing condition is with embodiment 1.
Catalyst after reduction is cooled to 150 DEG C in hydrogen atmosphere, introduces synthesis gas (gas space velocity 750h in reactor
-1hydrogen/carbon monoxide mole ratios 2.0), and system pressure is risen to 2.5MPa, rise to after required value until pressure, start recycle compressor and set up gas circulation (controlled circulation ratio is 8.5), and with the heating rate of 2 DEG C/h, bed mean temperature is risen to 190 DEG C, and at 190 DEG C constant temperature 24h, this, bed temperature distribution was in table 3 in stage.
Catalyst after constant temperature 24h, continues, with the heating rate of 1 DEG C/h, bed mean temperature is risen to 205 DEG C at 190 DEG C, and at 205 DEG C constant temperature 40h, this, bed temperature distribution was in table 3 in stage.
Catalyst after constant temperature 40h, continues, with the heating rate of 1 DEG C/h, bed mean temperature is risen to 218 DEG C at 205 DEG C, carries out Fischer-Tropsch synthesis at such a temperature and produces liquid hydrocarbon, and this stage bed temperature distribution is in table 3, and Fischer-Tropsch synthesis effect is in table 4.
The present embodiment Δ T1=2.3 DEG C, Δ T2=5.1 DEG C, Δ T3=7.7 DEG C, meet:
0℃＜ΔT1＜(1/2)ΔT2；(1/3)ΔT3＜ΔT2＜(2/3)ΔT3。Illustrate and adopt the method for the invention can realize steadily going into operation of F-T synthesis device.
Table 3 bed temperature distributes
| Bed mean temperature/DEG C | 190 | 205 | 218 |
| Thermocouple 1 | 189.0 | 203.0 | 214.7 |
| Thermocouple 2 | 189.9 | 205.5 | 218.2 |
| Thermocouple 3 | 191.3 | 208.1 | 222.4 |
| Thermocouple 4 | 190.1 | 205.4 | 219.7 |
| Thermocouple 5 | 189.5 | 204.3 | 217.1 |
| Thermocouple 6 | 189.1 | 203.9 | 215.7 |
| The bed temperature difference/DEG C | 2.3 | 5.1 | 7.7 |
Table 4 Fischer-Tropsch synthesis effect
| Reaction condition | |
| Mean temperature/DEG C | 218 |
| The bed temperature difference/DEG C | 7.7 |
| Hydrogen-carbon ratio | 2.0 |
| Recycle ratio | 8.5 |
| Pressure/MPa | 2.5 |
| Air speed/h -1 | 750 |
| Reaction effect | |
| CO conversion ratio/mol% | 89.11 |
| CH 4Selective/mol% | 8.93 |
| C 5+Selective/mol% | 86.60 |
Comparative example 1
After cobalt-based fixed bed FischerTropsch synthesis catalyst is loaded reactor, first reduce to catalyst in pure hydrogen atmosphere, reducing condition is with embodiment 1.
Catalyst after reduction is cooled to 150 DEG C in hydrogen atmosphere, introduces synthesis gas (gas space velocity 500h in reactor
-1hydrogen/carbon monoxide mole ratios 2.0), and system pressure is risen to 2.5MPa, rise to after required value until pressure, start recycle compressor and set up gas circulation (controlled circulation ratio is 8.0), and with the heating rate of 1 DEG C/h, bed mean temperature rising to 200 DEG C, constant temperature 1h has investigated bed temperature distribution and synthetic reaction effect at such a temperature, and concrete data are in table 5.
According to embodiment 1 result, temperature should be risen to 210 DEG C under this condition and just can reach higher conversion ratio, continue after 200 DEG C of constant temperature 1h with the heating rate of 1 DEG C/h to 210 DEG C of intensifications, but when temperature rises to 206 DEG C, beds overtemperature, unrealized object temperature being risen to 210 DEG C.
This comparative example is not applied method described in this patent and is gone into operation, and when temperature not yet rises to reaction temperature, overtemperature appears in beds.By during this comparative example average reaction temperature 200 DEG C bed temperature distribution and reaction effect compared with embodiment 1, when when can find out in comparative example 1 200 DEG C, CO conversion ratio is only 69.21%, its bed temperature difference just up to 7.6 DEG C, far above 6.1 DEG C when 4.0 in embodiment 1 when 200 DEG C DEG C and 210 DEG C.Illustrate and to go into operation without the method for the invention, beds focus is obvious, is unfavorable for steadily going into operation of device, and temperature rises to 206 DEG C and overtemperatures occur further illustrates this problem.
The distribution of table 5 bed temperature and reaction effect
| Bed mean temperature/DEG C | 200 |
| Thermocouple 1 | 196.3 |
| Thermocouple 2 | 200.6 |
| Thermocouple 3 | 203.9 |
| Thermocouple 4 | 200.7 |
| Thermocouple 5 | 199.6 |
| Thermocouple 6 | 198.5 |
| The bed temperature difference/DEG C | 7.6 |
| Reaction effect | |
| CO conversion ratio/mol% | 69.21 |
| CH 4Selective/mol% | 9.69 |
| C 5+Selective/mol% | 84.13 |
Comparative example 2
After cobalt-based fixed bed FischerTropsch synthesis catalyst is loaded reactor, first reduce to catalyst in pure hydrogen atmosphere, reducing condition is with embodiment 1.
Catalyst after reduction is cooled to 150 DEG C in hydrogen atmosphere, introduces synthesis gas (gas space velocity 500h in reactor
-1, hydrogen/carbon monoxide mole ratios 2.0), and system pressure is risen to 2.5MPa, rise to after required value until pressure, start recycle compressor and set up gas circulation (controlled circulation ratio is 8.0).With the heating rate of 1 DEG C/h, bed mean temperature is risen to 185 DEG C afterwards, at such a temperature constant temperature 24h, bed temperature distribution and reaction effect data are in table 6.
After 185 DEG C of constant temperature 24h, continue, with the heating rate of 1 DEG C/h, bed mean temperature is risen to 190 DEG C, constant temperature 24h at such a temperature, bed temperature distributed data is in table 6.Continue afterwards with the heating rate of 1 DEG C/h to 210 DEG C of intensifications, but when temperature rises to 208 DEG C, beds overtemperature, unrealized object temperature being risen to 210 DEG C.
As shown in Table 6, Δ T1=1.2 DEG C, Δ T2=1.8 DEG C in this example, according to embodiment 1 result, under the reaction conditions Δ T3=6.1 DEG C.In this example, the relation of Δ T2 and Δ T3 does not meet (1/3) Δ T3 < Δ T2 < (2/3) Δ T3.
Although this comparative example have passed through the active stabilization period in 185 DEG C and 190 DEG C two stages, but still there occurs overtemperature at 208 DEG C.As can be seen from CO conversion ratio when 185 DEG C and 190 DEG C, these two stage CO conversion ratios are all far below 88.92% in embodiment 1 during 210 DEG C of reactions, illustrate that the activated centre quantity of these two stage performance activity is all less, and under this operating mode, more active sites cannot be activated with passivation that it is just lived, in temperature-rise period after 190 DEG C, increasing active sites plays a role, but this stage does not have again the sufficient time by the passivation of amount of activated center, the overheating problem that final appearance is identical with comparative example 1.
This example further illustrates the importance of the T1 of Δ described in the present invention, Δ T2, Δ T3 relation, if triadic relation departs from relation of the present invention, even if catalyst is through low temperature just passivation alive, its passivation effect is non-optimal state also, finally still likely causes beds overtemperature.
The distribution of table 6 bed temperature and reaction effect
| Bed mean temperature/DEG C | 185 | 190 |
| Thermocouple 1 | 184.6 | 189.2 |
| Thermocouple 2 | 184.9 | 189.8 |
| Thermocouple 3 | 185.8 | 191.0 |
| Thermocouple 4 | 185.1 | 190.2 |
| Thermocouple 5 | 184.9 | 189.6 |
| Thermocouple 6 | 184.7 | 189.3 |
| The bed temperature difference/DEG C | 1.2 | 1.8 |
| Reaction effect | ||
| CO conversion ratio/mol% | 17.26 | 28.37 |
| CH 4Selective/mol% | 6.95 | 7.53 |
| C 5+Selective/mol% | 87.37 | 87.06 |
Claims (7)
1. a F-T synthesis device start-up method, comprises the following steps:
(1) fischer-tropsch synthetic catalyst reduces in reducibility gas;
(2) at beds axial temperature difference be Δ T1 operating condition under carry out Fischer-Tropsch synthesis 4 ~ 48h;
(3) at beds axial temperature difference be Δ T2 operating condition under carry out Fischer-Tropsch synthesis 4 ~ 48h;
(4) at beds axial temperature difference be Δ T3 operating condition under carry out Fischer-Tropsch synthesis, to produce liquid hydrocarbon;
The relation of described Δ T1, Δ T2, Δ T3 meets following condition: 0 DEG C of < Δ T1 < (1/2) Δ T2; (1/3) Δ T3 < Δ T2 < (2/3) Δ T3.
2. in accordance with the method for claim 1, it is characterized in that, described Δ T1 is 2 DEG C ~ 5 DEG C.
3. in accordance with the method for claim 1, it is characterized in that, described F-T synthesis device is fixed bed F-T synthesis device.
4. in accordance with the method for claim 1, it is characterized in that, described fischer-tropsch synthetic catalyst is Co based Fischer-Tropsch synthesis catalyst.
5. in accordance with the method for claim 1, it is characterized in that, the described catalyst reduction condition of step (1) is: temperature 300 ~ 600 DEG C, pressure 0.1 ~ 2.0MPa, gas hourly space velocity 300 ~ 3000h
-1.
6. in accordance with the method for claim 1, it is characterized in that, step (1) described reducibility gas is the mist of hydrogen or hydrogen and nitrogen, and in mist, the volume fraction of hydrogen is 2% ~ 99%.
7. in accordance with the method for claim 1, it is characterized in that, step (2) ~ described Fischer-Tropsch synthesis condition of step (4) is: temperature 170 ~ 280 DEG C, pressure 1.0 ~ 5.0MPa, fresh synthesis gas air speed 300 ~ 3000h
-1, fresh synthesis gas H:Cmoleratio 0.5 ~ 3.0, gas recycle ratio 1 ~ 10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185889A (en) * | 1977-07-27 | 1980-01-29 | Etat Francais Societe Anonyme de Telecommunication | Temperature gradient light waveguide |
| CN101747127A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method for fixed bed |
| CN101928194A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Tropsch synthesis method of fixed bed |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4185889A (en) * | 1977-07-27 | 1980-01-29 | Etat Francais Societe Anonyme de Telecommunication | Temperature gradient light waveguide |
| CN101747127A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method for fixed bed |
| CN101928194A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Tropsch synthesis method of fixed bed |
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