CN1297342C - Reduction method of syrup state bed Fischer Tropsch synthesis iron base catalyst - Google Patents
Reduction method of syrup state bed Fischer Tropsch synthesis iron base catalyst Download PDFInfo
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- CN1297342C CN1297342C CNB2004100645756A CN200410064575A CN1297342C CN 1297342 C CN1297342 C CN 1297342C CN B2004100645756 A CNB2004100645756 A CN B2004100645756A CN 200410064575 A CN200410064575 A CN 200410064575A CN 1297342 C CN1297342 C CN 1297342C
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Abstract
The present invention a stepping reduction method for a slurry state bed Fischer-Tropsch synthesis iron base catalyst. A slurry state bed reactor or prereduction reactor is added with hydrocarbon liquid phase medium and catalysts, and the catalyst content in the mixing slurry is from 3 wt% to 40 wt%. After air in a reactor system is completely replaced at normal temperature and pressure, the pressure of the reactor is raised to reduction pressure, and the temperature is raised to reduction temperature by programs; after the reduction temperature is reached, the catalyst is firstly reduced by pure H2 in the first step; then, in the second step, CO is used for reduction. After original position reduction is finished, the catalyst carries out Fischer-Tropsch synthesis reaction in the slurry state bed reactor; after the reduction out of the reactor is finished, the catalyst slurry is conveyed by a feeding pump or is pressed into the slurry state bed reactor with high pressure to carry out the Fischer-Tropsch synthesis reaction. The present invention has the advantages of simple method, medium activity, high stability and high anti-wear performance, and the catalyst granules are not damaged after reduction.
Description
Technical field
The invention belongs to a kind of method of reducing of catalyst, relate in particular to the original position or the outer step-by-step reduction method of device of the synthetic microspheric big particle industrial ferrum-based catalyst of Fischer-Tropsch in a kind of gas-liquid-solid three-phase paste state bed reactor.
Background technology
Synthetic synthesis gas (the H that makes by coal or natural gas that is meant of Fischer-Tropsch
2+ CO) in the course of reaction of synthetic hydrocarbon of catalyst and a small amount of organic oxygen-containing compound of by-product.The history in existing more than 80 year of the research of ferrum-based catalyst, this catalyst is because of having higher water gas shift reaction activity and advantage such as cheap and easy to get becomes with low hydrogen-carbon ratio (H
2/ CO mol ratio) coal based synthetic gas synthesizes one of important catalyst of Generation Liquid fluid fuel through Fischer-Tropsch.
But the sharpest edges of paste state bed reactor are reactor bed internal reaction things to be mixed, has good heat transfer performance, reaction temperature and control isothermal operation easily, thus available high average operation temperature and obtain higher reaction rate; Catalyst can online loading and unloading and can directly use low H when synthetic using paste state bed reactor to carry out Fischer-Tropsch in addition
2The coal based synthetic gas of/CO ratio, and paste state bed reactor has few relatively investment, bigger technology, economic advantages have been demonstrated, be the present synthetic liquid fuel technology (H.Schulz of focus development in the world, Applied Catalysis A:General 186 (1999) 3-12 and M.E.Dry, Applied Catalysis A:General 138 (1996) 319-344).
Paste state bed reactor has certain requirement to the granularity of catalyst, general particle size range is between 30-120 μ m, catalyst also need have certain wear resistance in addition, and the ON-LINE SEPARATION that is beneficial to product wax and catalyst is to guarantee the long-term stability operation of catalyst.
The ferrum-based catalyst of handling without reduction has the Fischer-Tropsch synthesis activity hardly.The thing of fresh ferrum-based catalyst mainly is α-Fe mutually
2O
3, α-Fe
2O
3Fischer-Tropsch synthesis almost there is not activity, but α-Fe
2O
3After reduction activation is handled phase transition can take place, generate α-Fe, Fe
3O
4With various cementite etc., and α-Fe, Fe
3O
4All be considered to have the Fischer-Tropsch synthesis activity with various cementite.The transformation of thing phase has tangible behavioral characteristics during the ferrum-based catalyst reduction, and closely related with reducing condition.The reduction pretreatment condition of ferrum-based catalyst (temperature, pressure, air speed, reducing gases composition, heating rate and pretreatment time etc.) has very big influence to catalyst reaction performance (activity, selectivity of product, stability and abrasion resistance), but various reducing conditions are also not fully aware of to the concrete corresponding relation that the catalyst reaction performance is exerted an influence, and are mutually related, the report of the preliminary treatment reduction process of suitable ferrum-based catalyst and method is very few.If it is improper that reducing condition is selected, even the catalyst of success preparation also can not get expected result in the running of syrup state bed Fischer Tropsch synthetic reaction so.So reasonably select the reduction pretreatment condition of slurry attitude bed ferrum-based catalyst, can make ferrum-based catalyst in Fischer-Tropsch synthesis, have suitable activity, reasonably selectivity, long stability and stronger abrasion resistance.
U.S. Texas A﹠amp; People such as the Bukur of M university are at magazine Applied catalysis, GeneralA:, 1999,186, a kind of slurry attitude bed Fe/Cu/K/SiO is disclosed among the 255-275
2The method of reducing of catalyst is specially: adopt pure H in the high pressure stirred tank of 1 liter
2, pure CO and H
2/ CO is a reducing gases than the synthesis gas that is 0.67, respectively to amorphous Fe/Cu/K/SiO
2Catalyst reduces processing.This method does not relate to the spray drying forming technology of catalyst, and catalyst granules is less and do not have regular shape, is unfavorable for the ON-LINE SEPARATION of Fischer-Tropsch synthetic pulp attitude bed reacting middle catalyst and wax.This article the longest reaction time of report only is 140 hours, the stability and the wear resistance of catalyst when considering long-time the running.
Chinese patent 200410012199.6 discloses a kind of reduction activation method of starching attitude bed ferrum-based catalyst, is specially fresh catalyst in the hydrocarbon liquids medium, feeds the synthesis gas temperature programmed reduction.What this method was used is one step of synthesis gas local reduction way.
U.S. Pat 4670414 discloses a kind of activation method that loads on the cobalt carbonyl catalyst on aluminium oxide or the silica, i.e. reduction → oxidation → reduction three-step approach.The reducing gases that adopts is H
2With N
2Gaseous mixture reduction, pure H
2And oxygen-containing gas.U.S. Pat 4413064 also discloses similar method of reducing.
People such as U.S. Davis are at magazine Fuel Processing Technology, and 2003,1672, a kind of method of reducing of starching attitude bed Fe/K/Si catalyst is disclosed among the 1-17, be specially: in the stirring arm state bed reactor of 1 liter, adopt pure H
2, pure CO and synthesis gas be respectively reducing gases catalyst carried out step reduction.This method of reducing has used the catalyst of spray drying forming technology preparation, and the synthetic running reaction time of Fischer-Tropsch is 400-1000 hour, but does not relate to wear resistance.
Summary of the invention
The purpose of this invention is to provide a kind of original position or outer step-by-step reduction method of device that is suitable for the synthetic microspherical iron-based catalyst of syrup state bed Fischer Tropsch of industrial mass production.
Step-by-step reduction method of the present invention is as follows:
(1) in paste state bed reactor or prereduction reactor, adds boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 3-40wt% in the slurries, be preferably 6-25wt%, the mechanical agitation in paste state bed reactor or the prereduction reactor or by gas distributor produce successively upwards the minute bubbles of bubbling catalyst is uniformly dispersed in the slurries of reactor;
(2) with inert gas, N
2Or pure H
2At normal temperatures and pressures that the air displacement in paste state bed reactor or the prereduction reactor assembly is complete, then at inert gas, N
2Or pure H
2Pressure with paste state bed reactor or prereduction reactor under the atmosphere is raised to reduction pressure 0.01-3.0MPa, best 0.05-1.5MPa, and gas space velocity is 500-2000h when boosting
-1, be preferably 1000-2000h
-1
(3) keep gas space velocity constant, with 0.2-4 ℃/minute, the heating rate that is preferably 0.2-1 ℃/minute is heated to 100-150 ℃ with paste state bed reactor or prereduction reactor then, preferably 110-120 ℃, and under this temperature range, stopped 2-8 hour preferably 3-5 hour; And then with 0.05-2 ℃/minute, the heating rate that is preferably 0.05-0.25 ℃/minute is warmed up to reduction temperature 210-320 ℃ with paste state bed reactor or prereduction reactor, is preferably 240-300 ℃;
(4) as use inert gas or N as described in the step (3)
2During intensification, paste state bed reactor or prereduction reactor are at inert gas or N
2Stop when being heated to reduction temperature under the atmosphere to paste state bed reactor or logical inert gas of prereduction reactor or N
2, feed pure H to paste state bed reactor or prereduction reactor then
2, regulate pure H
2Gas space velocity is 500-4000h
-1, be preferably 1000-3000h
-1As the pure H of use as described in the step (3)
2During intensification, regulate pure H
2Gas space velocity is 500-4000h
-1, be preferably 1000-3000h
-1Catalyst is at reduction temperature and pure H
2The following recovery time of atmosphere is 5-50 hour, is preferably 10-24 hour;
(5) pure H
2After reduction finishes, keep reduction temperature constant, feed synthesis gas, the mol ratio H of synthesis gas to paste state bed reactor or prereduction reactor then
2/ CO=0.5-2.5 is preferably 0.6-2.0, and regulating the synthesis gas air speed is 500-4000h
-1, be preferably 1000-3000h
-1, paste state bed reactor or prereduction reactor were handled 5-50 hour under synthesis gas atmosphere, were preferably 10-24 hour;
(6) as described in step (1)～(5) during use paste state bed reactor in-situ reducing catalyst, after the synthesis gas reduction finishes, keep the pressure of synthesis gas air speed and reactor assembly constant, the temperature of paste state bed reactor is heated up or cool to the synthetic initial reaction temperature of Fischer-Tropsch with 0.05-2 ℃/minute intensification or rate of temperature fall, the pressure of conditioned reaction system, air speed and synthesis gas proportioning begin Fischer-Tropsch synthesis to the initial reaction condition that Fischer-Tropsch synthesizes then; As described in step (1)～(5) during use prereduction reactor reducing catalyst, after the synthesis gas reduction finishes, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05-2 ℃/minute rate of temperature fall with the greenhouse cooling of prereduction reactor to 100-200 ℃, the catalyst pulp that this is reduced pumps in the paste state bed reactor with slurry pump or utilizes the pressure differential of prereduction reactor and paste state bed reactor that catalyst pulp is pressed into and begins Fischer-Tropsch synthesis in the paste state bed reactor then.
Aforesaid catalyst is a ferrum-based catalyst, and catalyst master metal active component is an iron, and auxiliary agent is copper, potassium, manganese, zinc, rare earth element, silica and alundum (Al.
Aforesaid synthesis gas is by H
2Form H with CO
2With the mol ratio of CO be H
2/ CO=0.5-2.5 is preferably 0.6-2.0.
Advantage of the present invention:
Catalyst both can be in the gas-liquid-solid three-phase paste state bed reactor in-situ reducing, also can in the prereduction reactor, reduce.Catalyst simplified operation step during in-situ reducing in paste state bed reactor, method is simple.When catalyst reduces in the prereduction reactor, because of the capacity of prereduction reactor less, so the easier control of reducing condition; In the fischer-tropsch reaction running, be easy to the deficiency of catalyst in the online additional paste state bed reactor; Relatively harsher when reducing condition, when needing the HTHP reduction, use the prereduction reactor can reduce equipment cost, energy efficient.
2. catalyst is used H earlier
2Reduction is handled with synthesis gas again, can slow down the carbonizing degree of catalyst, reduces the generation of catalyst surface carbon distribution.
3. reduction rear catalyst particle is not damaged, and is active moderate, good stability, and wear resistance is strong.The specific embodiment
Describe several specific embodiments of the present invention below in detail, protection scope of the present invention is not subjected to the restriction of these embodiment.
The product collection method and the analysis test method of the Fischer-Tropsch synthesis system that the embodiment of the invention is used:
1. the product collection method of reaction system: unstripped gas measures with mass flowmenter, wax phase heavy hydrocarbon product is collected by wax trap (180 ℃), oil phase and water-phase product are collected by hot trap (105 ℃) and cold-trap (0 ℃), gas-phase product emptying after the wet flow indicator metering that can't condensation.Gathered a product in per 24 hours and calculated material balance, tail gas guaranteed the analysis more than 3 times during thing was flat, and thing is flat to remain on about 97%.
2. product analysis method: CO2 adopts the external standard method on-line analysis in the tail gas, is chromatographic column with Hayesep N, and TCD detects.Other product H in the tail gas
2, O
2, N
2, CH
4With the CO on-line analysis, adopting the 5A molecular sieve is that (30m * 0.53mm), TCD detects chromatographic column.C1～C8 hydrocarbon adopts the Al2O3 fused-silica capillary column, and (50m * 0.53mm) analyze, FID detects.Gas-phase product is analyzed data and is handled with the correction normalization method of methane association.Liquid product adopts the DB-1 fused-silica capillary column, and (60m * 0.25mm) (30m * 0.25mm) analyze, FID detects with the DB-WAX fused-silica capillary column.The wax phase product adopts UV+-(HT) fused-silica capillary column, and (30m * 0.53mm) analyze, FID detects.
3. the breakage rate of catalyst: with the method for SEM to catalyst reduction after and reacted spherical morphology observe and count, breakage rate calculates by ground grains number in each hundred particle, counts 500 more than the catalyst granules at every turn.
Embodiment 1:
1. in paste state bed reactor, add boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 8wt% in the slurries, the mechanical agitation in the paste state bed reactor or by gas distributor produce constantly continuously upwards the minute bubbles of bubbling catalyst is evenly disperseed in the slurries of reactor;
2. at normal temperatures and pressures that the intrasystem air displacement of paste state bed reactor is complete with inert gas, under inert gas atmosphere, the pressure of paste state bed reactor is raised to 0.1MPa then, gas space velocity is 500h when boosting
-1
3. regulating the inert gas air speed is 3000h
-1, with 0.2 ℃/minute heating rate the temperature of paste state bed reactor is heated to 100 ℃ then, and under this temperature range, stopped 3 hours, and then paste state bed reactor is warmed up to 240 ℃ with 0.1 ℃/minute heating rate;
4. stop to the logical inert gas of paste state bed reactor, beginning feeds pure H to paste state bed reactor
2Regulate pure H
2Gas space velocity is 1000h
-1
5. paste state bed reactor is at 240 ℃, pure H
2Reduction is 15 hours under the atmosphere;
6. stop to feed pure H to paste state bed reactor
2, keep reduction temperature and pressure constant, feed synthesis gas to paste state bed reactor then, the mol ratio of synthesis gas is H
2With the mol ratio of CO be H
2/ CO=1.0, regulating the synthesis gas air speed is 1000h
-1, paste state bed reactor was handled 25 hours under synthesis gas atmosphere;
Catalyst in paste state bed reactor through pure H
2After reduction finishes with synthesis gas, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05 ℃/minute heating rate the temperature of paste state bed reactor is warmed up to 250 ℃ of the synthetic initial reaction temperature of Fischer-Tropsch,, the pressure of conditioned reaction system is to 1.5MPa, synthesis gas proportioning H then
2/ CO=0.70 (mol ratio) and synthesis gas air speed are 2000h
-1, the beginning Fischer-Tropsch synthesis.In the reaction, unstripped gas measures with mass flowmenter, and wax phase heavy hydrocarbon product is collected by wax trap (180 ℃), and oil phase and water-phase product are collected by hot trap (105 ℃) and cold-trap (0 ℃), gas-phase product emptying after wet flow indicator measures that can't condensation.This catalyst reduction process is labeled as A, and Fischer-Tropsch synthesis performance evaluation the results are shown in subordinate list.
Embodiment 2:
1. in paste state bed reactor, add boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 10wt% in the slurries, the mechanical agitation in the paste state bed reactor or by gas distributor produce constantly continuously upwards the minute bubbles of bubbling catalyst is evenly disperseed in the slurries of reactor;
2. use H
2At normal temperatures and pressures that the intrasystem air displacement of paste state bed reactor is complete, then at H
2Pressure with paste state bed reactor under the atmosphere is raised to 0.5MPa, and gas space velocity is 1000h when boosting
-1
3. regulating the H2 air speed is 2000h
-1With 0.2 ℃/minute heating rate the temperature of paste state bed reactor is heated to 120 ℃ then, and under this temperature range, stopped 5 hours, and then paste state bed reactor is warmed up to 260 ℃ with 0.1 ℃/minute heating rate, and under this temperature and atmosphere reductase 12 5 hours;
4. stop to feed pure H to paste state bed reactor
2, keep reduction temperature and pressure constant, feed synthesis gas to paste state bed reactor then, the mol ratio of synthesis gas is H
2/ CO=1.5, regulating the synthesis gas air speed is 2000h
-1, paste state bed reactor was handled 15 hours under synthesis gas atmosphere;
Catalyst in paste state bed reactor through pure H
2After reduction finishes with synthesis gas, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05 ℃/minute rate of temperature fall with the greenhouse cooling of paste state bed reactor to 250 ℃ of the synthetic initial reaction temperature of Fischer-Tropsch, the pressure of conditioned reaction system is to 1.5MPa, synthesis gas proportioning H then
2/ CO=0.70 (mol ratio) and synthesis gas air speed are 2000h
-1, the beginning Fischer-Tropsch synthesis.In the reaction, unstripped gas measures with mass flowmenter, and wax phase heavy hydrocarbon product is collected by wax trap (180 ℃), and oil phase and water-phase product are collected by hot trap (105 ℃) and cold-trap (0 ℃), gas-phase product emptying after wet flow indicator measures that can't condensation.This catalyst reduction process is labeled as B, and Fischer-Tropsch synthesis performance evaluation the results are shown in subordinate list.
Embodiment 3:
1. in the prereduction reactor, add boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 15wt% in the slurries, the mechanical agitation in the prereduction reactor or by gas distributor produce constantly continuously upwards the minute bubbles of bubbling catalyst is evenly disperseed in the slurries of reactor;
2. use N
2At normal temperatures and pressures that intrasystem air displacement in the prereduction reactor is complete, then at N
2Under the atmosphere pressure in the prereduction reactor is raised to 1.0MPa, gas space velocity is 500h when boosting
-1
3. regulating the N2 air speed is 2000h
-1, with the heating rate of 1/ minute ℃ of clock the temperature of prereduction reactor is heated to 150 ℃ then, and under this temperature range, stopped 6 hours, and then the prereduction reactor is warmed up to 250 ℃ with 0.1 ℃/minute heating rate;
4. stop to the logical N of prereduction reactor
2, beginning feeds pure H to the prereduction reactor
2Regulate pure H
2Gas space velocity is 1000h
-1
5. paste state bed reactor is at 250 ℃, pure H
2Reduction is 5 hours under the atmosphere;
6. stop to feed pure H to the prereduction reactor
2, keep reduction temperature and pressure constant, feed synthesis gas to the prereduction reactor then, the mol ratio of synthesis gas is H
2/ CO=1.2, regulating the synthesis gas air speed is 1000h
-1, the prereduction reactor was handled 20 hours under synthesis gas atmosphere;
Catalyst in the prereduction reactor through pure H
2After reduction finishes with synthesis gas, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05 ℃/minute rate of temperature fall the temperature of prereduction reactor is dropped to 150 ℃, this catalyst pulp that reduces is pumped in the paste state bed reactor (paste state bed reactor heat in advance be forced into 150 ℃, 1.0MPa) with slurry pump then, the pressure of conditioned reaction system is to 1.5MPa, synthesis gas proportioning H then
2/ CO=0.70 (mol ratio) and synthesis gas air speed are 2000h
-1, the beginning Fischer-Tropsch synthesis.In the reaction, unstripped gas measures with mass flowmenter, and wax phase heavy hydrocarbon product is collected by wax trap (180 ℃), and oil phase and water-phase product are collected by hot trap (105 ℃) and cold-trap (0 ℃), gas-phase product emptying after wet flow indicator measures that can't condensation.This catalyst reduction process is labeled as C, and Fischer-Tropsch synthesis performance evaluation the results are shown in subordinate list.
Embodiment 4:
1. in the prereduction reactor, add boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 20wt% in the slurries, the mechanical agitation in the prereduction reactor or by gas distributor produce constantly continuously upwards the minute bubbles of bubbling catalyst is evenly disperseed in the slurries of reactor;
2. use H
2At normal temperatures and pressures that intrasystem air displacement in the prereduction reactor is complete, then at H
2Under the atmosphere pressure in the prereduction reactor is raised to 1.2MPa, gas space velocity is 500h-1 when boosting.
3. regulating the H2 air speed is 2000h
-1, with 0.5 ℃/minute heating rate the temperature of prereduction reactor is heated to 150 ℃ then, and under this temperature range, stopped 6 hours, and then the prereduction reactor is warmed up to 290 ℃ with 0.1 ℃/minute heating rate; Prereduction reactor reductase 12 4 hours under this temperature and atmosphere;
4. stop to feed pure H2 to the prereduction reactor, keep reduction temperature and pressure constant, feed synthesis gas to the prereduction reactor then, the mol ratio of synthesis gas is H
2/ CO=2.0, regulating the synthesis gas air speed is 1000h
-1, the prereduction reactor was handled 24 hours under synthesis gas atmosphere;
Catalyst in the prereduction reactor through pure H
2After reduction finishes with synthesis gas, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05 ℃/minute rate of temperature fall the temperature of prereduction reactor is dropped to 120 ℃, this catalyst pulp that reduces is pumped in the paste state bed reactor (paste state bed reactor heat in advance be forced into 120 ℃, 1.2MPa) with slurry pump then, the pressure of conditioned reaction system is to 1.5MPa, synthesis gas proportioning H then
2/ CO=0.70 (mol ratio) and synthesis gas air speed are 2000h
-1, the beginning Fischer-Tropsch synthesis.In the reaction, unstripped gas measures with mass flowmenter, and wax phase heavy hydrocarbon product is collected by wax trap (180 ℃), and oil phase and water-phase product are collected by hot trap (105 ℃) and cold-trap (0 ℃), gas-phase product emptying after wet flow indicator measures that can't condensation.This catalyst reduction process is labeled as D, and Fischer-Tropsch synthesis performance evaluation the results are shown in subordinate list.
Embodiment 5:
1. in the prereduction reactor, add boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 25wt% in the slurries, the mechanical agitation in the prereduction reactor or by gas distributor produce constantly continuously upwards the minute bubbles of bubbling catalyst is evenly disperseed in the slurries of reactor;
2. use H
2At normal temperatures and pressures that intrasystem air displacement in the prereduction reactor is complete, then at H
2Under the atmosphere pressure in the prereduction reactor is raised to 2.0MPa, gas space velocity is 500h when boosting
-1
3. regulate H
2Air speed is 2000h
-1, with 0.5 ℃/minute heating rate the temperature of prereduction reactor is heated to 150 ℃ then, and under this temperature range, stopped 4 hours, and then the prereduction reactor is warmed up to 300 ℃ with 0.1 ℃/minute heating rate; Prereduction reactor reductase 12 0 hour under this temperature and atmosphere;
4. stop to feed pure H to the prereduction reactor
2, keep reduction temperature and pressure constant, feed synthesis gas to the prereduction reactor then, the mol ratio of synthesis gas is H
2/ CO=1.23, regulating the synthesis gas air speed is 1000h
-1, the prereduction reactor was handled 12 hours under synthesis gas atmosphere;
Catalyst in the prereduction reactor through pure H
2After reduction finishes with synthesis gas, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05 ℃/minute rate of temperature fall the temperature of prereduction reactor is dropped to 160 ℃, the pressure differential of utilizing prereduction reactor and paste state bed reactor then is pressed into this catalyst pulp that reduces in the paste state bed reactor (paste state bed reactor heat in advance be forced into to 160 ℃, 1.5MPa), regulates synthesis gas proportioning H then
2/ CO=0.70 (mol ratio) and synthesis gas air speed are 2000h
-1, the beginning Fischer-Tropsch synthesis.In the reaction, unstripped gas measures with mass flowmenter, and wax phase heavy hydrocarbon product is collected by wax trap (180 ℃), and oil phase and water-phase product are collected by hot trap (105 ℃) and cold-trap (0 ℃), gas-phase product emptying after wet flow indicator measures that can't condensation.This catalyst reduction process is labeled as E, and Fischer-Tropsch synthesis performance evaluation the results are shown in subordinate list.
Reduction of subordinate list embodiment 1-5 catalyst original position and Fischer-Tropsch synthesis evaluation result
| A | Running time, hour | 0 | 100 | 300 | 500 | 1000 | 1500 | 2000 | 2500 |
| The CO conversion ratio, % | - | 48.21 | 52.16 | 53.05 | 52.78 | 52.11 | 50.95 | 49.63 | |
| CH 4Selectivity, wt% | - | 4.96 | 4.92 | 4.69 | 4.62 | 4.73 | 4.97 | 5.04 | |
| C 5 +Selectivity, wt% | - | 72.82 | 73.58 | 74.80 | 75.33 | 74.88 | 73.77 | 73.01 | |
| Deactivation rate, %/sky | - | - | - | - | - | 0.03 | 0.06 | 0.06 | |
| Reduction back breakage rate, % | 0.01 | - | - | - | - | - | - | - | |
| Reaction back breakage rate, % | 0 | 0 | 0 | 0 | 0 | 0 | 0.1 | 0.4 | |
| B | Running time, hour | 0 | 100 | 300 | 500 | 800 | 1000 | 1200 | 1600 |
| The CO conversion ratio, % | - | 56.20 | 58.33 | 59.21 | 60.17 | 59.83 | 59.21 | 58.01 | |
| CH 4Selectivity, wt% | - | 5.39 | 5.13 | 5.24 | 4.97 | 5.00 | 5.26 | 5.36 | |
| C 5 +Selectivity, wt% | - | 70.87 | 72.62 | 71.92 | 73.44 | 73.63 | 71.72 | 70.45 | |
| Deactivation rate, %/sky | - | - | - | - | - | - | 0.24 | 0.08 | |
| Reduction back breakage rate, % | 0 | - | - | - | - | - | - | - | |
| Reaction back breakage rate, % | - | 0 | 0 | 0 | 0 | 0 | 0 | 0.15 | |
| C | Running time, hour | 0 | 100 | 500 | 1000 | 2000 | 3000 | 4000 | 5000 |
| The CO conversion ratio, % | - | 49.23 | 55.94 | 55.80 | 53.21 | 51.16 | 49.01 | 46.28 | |
| CH 4Selectivity, wt% | - | 5.23 | 5.58 | 5.61 | 5.40 | 5.39 | 5.16 | 5.12 | |
| C 5 +Selectivity, wt% | - | 75.71 | 70.46 | 69.73 | 71.03 | 70.87 | 72.59 | 73.14 | |
| Deactivation rate, %/sky | - | - | - | - | 0.06 | 0.05 | 0.05 | 0.07 | |
| Reduction back breakage rate, % | 0 | - | - | - | - | - | - | - | |
| Reaction back breakage rate, % | 0 | 0 | - | 0 | 0.1 | 0.1 | 0.65 | 1.13 | |
| D | Running time, hour | 0 | 100 | 500 | 1000 | 1500 | 2000 | 2500 | 3000 |
| The CO conversion ratio, % | - | 55.33 | 56.25 | 57.44 | 56.18 | 55.23 | 54.01 | 53.21 | |
| CH 4Selectivity, wt% | - | 4.92 | 5.34 | 5.52 | 5.46 | 5.19 | 5.49 | 5.34 | |
| C 5 +Selectivity, wt% | - | 73.48 | 71.86 | 70.47 | 70.89 | 72.08 | 70.98 | 71.69 | |
| Deactivation rate, %/sky | - | - | - | - | 0.06 | 0.05 | 0.06 | 0.04 | |
| Reduction back breakage rate, % | 0 | - | - | - | - | - | - | - | |
| Reaction back breakage rate, % | 0 | - | - | - | - | 0.1 | 0.4 | 0.7 | |
| E | Running time, hour | 0 | 100 | 500 | 1000 | 1500 | 2000 | 2300 | 2500 |
| The CO conversion ratio, % | - | 43.15 | 48.55 | 52.11 | 52.23 | 51.08 | 50.04 | 49.33 | |
| CH 4Selectivity, wt% | - | 5.21 | 5.36 | 5.61 | 5.39 | 5.43 | 5.54 | 5.57 | |
| C 5 +Selectivity, wt% | - | 71.55 | 71.45 | 70.46 | 71.25 | 70.72 | 71.21 | 70.48 | |
| Deactivation rate, %/sky | - | - | - | - | - | 0.05 | 0.08 | 0.09 | |
| Reduction back breakage rate, % | 0 | - | - | - | - | - | - | - | |
| Reaction back breakage rate, % | - | 0 | 0 | 0 | 0 | 0.2 | 0.3 | 0.55 |
Annotate: represent 0 hour running time in-situ reducing to finish, do not begin Fischer-Tropsch synthesis as yet.
Claims (12)
1. the method for reducing of a syrup state bed Fischer Tropsch synthesis iron base catalyst is characterized in that comprising the steps:
(1) in paste state bed reactor or prereduction reactor, adds boiling point greater than 340 ℃ hydrocarbon compound liquid and fresh ferrum-based catalyst, the content of catalyst is 3-40wt% in the slurries, the mechanical agitation in paste state bed reactor or the prereduction reactor or by gas distributor produce successively upwards the minute bubbles of bubbling catalyst is uniformly dispersed in the slurries of reactor;
(2) with inert gas, N
2Or pure H
2At normal temperatures and pressures that the air displacement in paste state bed reactor or the prereduction reactor assembly is complete, then at inert gas, N
2Or pure H
2Pressure with paste state bed reactor or prereduction reactor under the atmosphere is raised to reduction pressure 0.01-3.0MPa, and gas space velocity is 500-2000h when boosting
-1
(3) keep gas space velocity constant, with 0.2-4 ℃/minute heating rate paste state bed reactor or prereduction reactor are heated to 100-150 ℃ then, and under this temperature range, stopped 2-8 hour; And then paste state bed reactor or prereduction reactor are warmed up to reduction temperature 210-320 ℃ with 0.05-2 ℃/minute heating rate;
(4) as use inert gas or N as described in the step (3)
2During intensification, paste state bed reactor or prereduction reactor are at inert gas or N
2Stop when being heated to reduction temperature under the atmosphere to paste state bed reactor or logical inert gas of prereduction reactor or N
2, feed pure H to paste state bed reactor or prereduction reactor then
2, regulate pure H
2Gas space velocity is 500-4000h
-1As the pure H of use as described in the step (3)
2During intensification, regulate pure H
2Gas space velocity is 500-4000h
-1Catalyst is at reduction temperature and pure H
2The following recovery time of atmosphere is 5-50 hour;
(5) pure H
2After reduction finishes, keep reduction temperature constant, feed synthesis gas, the mol ratio H of synthesis gas to paste state bed reactor or prereduction reactor then
2/ CO=0.5-2.5, regulating the synthesis gas air speed is 500-4000h
-1, paste state bed reactor or prereduction reactor were handled 5-50 hour under synthesis gas atmosphere;
(6) as described in step (1)～(5) during use paste state bed reactor in-situ reducing catalyst, after the synthesis gas reduction finishes, keep the pressure of synthesis gas air speed and reactor assembly constant, the temperature of paste state bed reactor is heated up or cool to the synthetic initial reaction temperature of Fischer-Tropsch with 0.05-2 ℃/minute intensification or rate of temperature fall, the pressure of conditioned reaction system, air speed and synthesis gas proportioning begin Fischer-Tropsch synthesis to the initial reaction condition that Fischer-Tropsch synthesizes then; As described in step (1)～(5) during use prereduction reactor reducing catalyst, after the synthesis gas reduction finishes, keep the pressure of synthesis gas air speed and reactor assembly constant, with 0.05-2 ℃/minute rate of temperature fall with the greenhouse cooling of prereduction reactor to 100-200 ℃, the catalyst pulp that this is reduced pumps in the paste state bed reactor with slurry pump or utilizes the pressure differential of prereduction reactor and paste state bed reactor that catalyst pulp is pressed into and begins Fischer-Tropsch synthesis in the paste state bed reactor then.
2, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that the content of catalyst in the middle slurries of described step (1) is 6-25wt%.
3, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that reduction pressure is 0.05-1.5MPa in the described step (2).
4, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that gas space velocity is 1000-2000h in the described step (2)
-1
5, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1, it is characterized in that keeping in the described step (3) gas space velocity constant, with 0.2-1 ℃/minute heating rate paste state bed reactor or prereduction reactor are heated to 110-120 ℃ then, and under this temperature range, stopped 3-5 hour; And then paste state bed reactor or prereduction reactor are warmed up to reduction temperature 240-300 ℃ with 0.05-0.25 ℃/minute heating rate.
6, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that in the described step (4) as use inert gas or N as described in the step (3)
2During intensification, pure H
2Gas space velocity is 1000-3000h
-1
7, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that in the described step (4) as the pure H of use as described in the step (3)
2During intensification, pure H
2Gas space velocity is 1000-3000h
-1
8, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that the catalyst reduction time is 10-24 hour in the described step (4).
9, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that the mol ratio of synthesis gas in the described step (5) is H
2/ CO=0.6-2.0.
10, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that the synthesis gas air speed is 1000-3000h in the described step (5)
1
11, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that middle paste state bed reactor of described step (5) or prereduction reactor are 10-24 hour in the synthesis gas following processing time of atmosphere.
12, the method for reducing of a kind of syrup state bed Fischer Tropsch synthesis iron base catalyst as claimed in claim 1 is characterized in that described ferrum-based catalyst master metal active component is an iron, and auxiliary agent is copper, potassium, manganese, zinc, rare earth element, silica or alundum (Al.
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| WO2010075047A2 (en) * | 2008-12-23 | 2010-07-01 | Rentech, Inc. | Catalyst activation in fischer-tropsch processes |
| JP5730495B2 (en) * | 2010-03-30 | 2015-06-10 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for producing activated catalyst for Fischer-Tropsch synthesis reaction, method for producing catalyst slurry, and method for supplying catalyst slurry to Fischer-Tropsch synthesis reactor |
| CN102553657B (en) * | 2012-01-06 | 2013-11-20 | 神华集团有限责任公司 | Reduction method of fischer tropsch catalyst |
| CN104549559B (en) * | 2013-10-28 | 2017-03-15 | 中国石油化工股份有限公司 | Fluid bed syngas directly prepare the activation method of low-carbon alkene ferrum-based catalyst |
| CN106552632B (en) * | 2015-09-30 | 2019-04-16 | 神华集团有限责任公司 | A kind of restoring method of Fischer-Tropsch synthetic iron-based catalyst |
| CN108654654B (en) * | 2017-04-01 | 2021-09-03 | 国家能源投资集团有限责任公司 | Precipitated iron Fischer-Tropsch catalyst and preparation method and application thereof |
| CN109663597A (en) * | 2018-12-18 | 2019-04-23 | 中国科学院上海高等研究院 | A method of the in-situ reducing activation method and alkene directly processed of the cobalt-containing catalyst for slurry bed system synthesis gas alkene directly processed |
| CN114471744B (en) * | 2020-11-13 | 2023-09-19 | 珠海市福沺能源科技有限公司 | Pretreatment method of iron-based catalyst and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413064A (en) * | 1981-10-13 | 1983-11-01 | Gulf Research & Development Company | Fluid bed catalyst for synthesis gas conversion and utilization thereof for preparation of diesel fuel |
| US4670414A (en) * | 1981-10-13 | 1987-06-02 | Kobylinski Thaddeus P | Activated cobalt catalyst and synthesis gas conversion using same |
| US20040152791A1 (en) * | 2002-11-25 | 2004-08-05 | Zyl Andre Johan Van | Catalyst |
-
2004
- 2004-11-30 CN CNB2004100645756A patent/CN1297342C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4413064A (en) * | 1981-10-13 | 1983-11-01 | Gulf Research & Development Company | Fluid bed catalyst for synthesis gas conversion and utilization thereof for preparation of diesel fuel |
| US4670414A (en) * | 1981-10-13 | 1987-06-02 | Kobylinski Thaddeus P | Activated cobalt catalyst and synthesis gas conversion using same |
| US20040152791A1 (en) * | 2002-11-25 | 2004-08-05 | Zyl Andre Johan Van | Catalyst |
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