CN1079701C - Catalyst activation process and catalyst reactivation process - Google Patents
Catalyst activation process and catalyst reactivation process Download PDFInfo
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- CN1079701C CN1079701C CN95120515A CN95120515A CN1079701C CN 1079701 C CN1079701 C CN 1079701C CN 95120515 A CN95120515 A CN 95120515A CN 95120515 A CN95120515 A CN 95120515A CN 1079701 C CN1079701 C CN 1079701C
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Abstract
Process for activation or re-activation of a Fischer-Tropsch catalyst packed in a bed by contacting the catalyst prior to operation with a reducing gas at a temperature below 500 DEG C, characterized in that the reducing gas is passed through the catalyst bed in a direction reversed to the direction of the flow of reactants during operation. Process for activation or reactivation of an at least partially deactivated Fischer-Tropsch catalyst packed in a bed comprising the successive steps of:(a)contacting the catalyst with a reducing gas;(b)contacting the catalyst with an oxidising gas; and(c)reducing the catalyst via the (re-)activation process described above.
Description
The present invention relates to a kind ofly change into the activation method of the catalyst that uses in the reaction of hydrocarbon at carbon monoxide and hydrogen mixed gas.The present invention also relates to use afterwards and to the small part inactivation, it is carried out the method for reactivation at this catalyst.
Usually be referred to as Fischer-Tropsch synthesis in the method that in the presence of suitable catalyst, from carbon monoxide and hydrogen mixture, prepares hydrocarbon under high temperature and the high pressure.The catalyst that uses in this hydrocarbon is synthetic is referred to as Fischer-Tropsch catalyst usually, and it generally includes one or more metals that is selected from VIII family in the periodic table of elements, reaches one or more nonessential co-catalysts and typically comprises carrier material.In order to be suitable at H
2/ CO gaseous mixture is transformed in the reaction of hydrocarbon and uses, and usually Fischer-Tropsch catalyst is at first carried out activation processing.Activation process normally with catalyst with reducing gas, contact as hydrogen-containing gas.
For example, at US-A-4, a kind of method for preparing Fischer-Tropsch catalyst is disclosed in 413,064, wherein after last impregnation stage, about 250 ℃～400 ℃ in the presence of hydrogen lentamente reducing catalyst make it activation.Sources of hydrogen can be the mixture of pure hydrogen or hydrogen and nitrogen.Similarly, at EP-A-0,168, the method of another kind of activation Fischer-Tropsch catalyst is disclosed in 894, this method comprises makes catalyst at high temperature contact with a kind of hydrogen-containing gas, and wherein hydrogen partial pressure carries out gradually from start to finish or progressively increases, and its final value is at least five times of initial value.US-A-4, the activation process in 413,064 and EP-A-0,168,894 all is to carry out before catalyst is loaded into fixed bed.
The in-situ activation of catalyst, promptly catalyst is loaded at it and activates after carrying out in the synthetic reactor of Fischer-Tropsch, is a kind of already known processes.It comprises make in operation reducing gases (normally hydrogen-containing gas with the direction identical with reactant flow by catalyst bed, thereby the activating catalyst particle.One of shortcoming of this method is that catalyst activity decreases along gas flow direction.This mainly is owing to generated water when torpescence VIII family metallic compound is reduced into its catalytic activity form.Therefore the air-flow that leaves reactor after exit flow, the i.e. activation contains moisture content.The water that generates passes through catalyst bed with reducing gases.But under the situation of not wishing to be subjected to the particular theory restriction, thereby the reduction degree on the direction of reducing gas stream of the water resistance reduction that ends VIII family metallic compound seemingly reduces, thereby has reduced activity of such catalysts.Therefore, in normal running, the level of conversion ratio also reduces along the reacting gas flow path direction.This point can be verified by measure its temperature curve along catalyst bed.F-T synthesis reaction is strong exothermic process, therefore has big calorimetric to produce.Temperature curve shows that the peak of temperature is the position that at first contact with reacting gas stream at catalyst bed, and temperature is along with reacting gas stream is further stopped the agent bed and reduced by urging.This shows that transform level is really along with reacting gas stream reduces by catalyst bed.
US-A-4 also recognizes this problem in 778,826.This patent relates to C
1-C
3Paraffinic feedstock changes into the more method of the hydrocarbon of HMW, and this method is at first to allow C
1-C
3Alkane and air react and form the gaseous mixture that contains carbon monoxide, hydrogen and nitrogen, by F-T synthesis reaction this gaseous mixture are changed into the more hydrocarbon of HMW subsequently.As a solution of the problem that above-mentioned in-situ activation is occurred, suggestion is carried out Fischer-Tropsch by admixture of gas being passed the microscler reactor that is surrounded by the Fischer-Tropsch catalyst bed
Synthetic reaction, wherein catalyst activity constantly rises to outlet from reactor inlet.According to US-A-4,778,826, three kinds of modes are arranged, can obtain this active rising gradient.The first, dilute fischer-tropsch catalyst particles with inert particle, wherein reduce to the outlet dilution factor from reactor inlet.The second, adopt thermograde along catalyst bed, wherein from the reactor inlet to the outlet temperature, increase.At last, increase the concentration of catalytic active component the catalyst granules to outlet from reactor inlet.The actual suitable activation method of catalyst granules is with reducing agent, particle is handled under 320-440 ℃ as hydrogen.In fact the way in practical operation be with reactor be heated to preference temperature and with hydrogen stream from top to bottom, promptly identical with reaction gas flow direction passes catalyst bed.
According to US-A-4,778,826 method obviously need be taked other measure, and for example the carefulness of catalyst bed loads, to guarantee to produce required active gradient.One of main purpose of the present invention is to exempt these addition thereto, still can reach more constant transform level at whole catalyst bed simultaneously.More particularly, the purpose of this invention is to provide a kind of activation method, wherein by increase the active active gradient that obtains along catalyst bed along the reaction gas flow direction.In addition, the objective of the invention is to make this activation method simple as far as possible, and the big cost of avoiding causing in order to reequip existing equipment spend.Obviously consider that from efficient and cost two aspects this meets the requirements.In fact, an object of the present invention is to provide a kind of activation method, it requires that hardly existing equipment is carried out any repacking but can obtain required active gradient along catalyst bed.
Therefore, a first aspect of the present invention relates to a kind of activation of the Fischer-Tropsch catalyst in the bed, preferred in-situ activation method of filling in, promptly by before operation, promptly allowing catalyst contact with reducing gas below 500 ℃ before the Fischer-Tropsch hydrocarbon building-up process of operation catalysis, it is opposite with the direction of reaction gas flow to it is characterized in that having reducing gases in the operation to pass through the direction of catalyst bed.
Fischer-Tropsch catalyst and preparation method thereof is a known technology.Usually this class catalyst is included in one or more metals that are selected from VIII family in the periodic table of elements on the suitable carrier and uses with one or more nonessential co-catalysts.Example of this class catalyst and preparation method thereof is disclosed in EP-A-0, and 428,223 and EP-A-0,510,771.The example of suitable catalyst has also been described in the specification of patent discussed above.
Preferred catalyst according to the inventive method activation or reactivation comprises cobalt, iron, nickel or ruthenium metallic compound or its mixture.Most preferred catalysts comprises cobalt metallic compound, especially cobalt oxide.
Metallic compound is carried on the catalyst carrier usually.The appropriate catalyst carrier can be selected from refractory oxide, preferred aluminium oxide, silica, titanium dioxide, zirconia or its mixture, more preferably silica, silica-zirconia blend, titanium dioxide or zirconia.
This metal that 1～100 part of heavy, preferred 10～50 parts of weight is arranged on the normally per 100 parts of heavy carrier materials of the amount of catalytically-active metals on the carrier.
Catalytically-active metals can together use with one or more metal promoters.Co-catalyst can exist with metal or metal oxide form, depends on used particular promoter.Suitable co-catalyst comprises the oxide of metal oxide, group of the lanthanides and/or the actinium series of IIA in the periodic table of elements, IIIB, IVB, VB, VIB and/or VIIB family.Preferred catalyst comprises oxide, especially titanium, zirconium, manganese and/or the vanadium of element in periodic table of elements IVB, VB and/or the VIIB family at least.As another component or except the co-catalyst of metal oxide, catalyst can comprise the metal promoters of selecting in from periodic table of elements VIIB and/or the VII family.Preferred metal promoters comprises rhenium, platinum and palladium.
Only catalyst comprises that cobalt is made catalytically-active metals and zirconium is made co-catalyst.Another optimum catalyst comprises that cobalt makes catalytically-active metals and manganese and/or vanadium and make co-catalyst.
If have co-catalyst in the catalyst, then its amount is generally promoter 0.1～60 part heavy, preferred 0.5～40 part of weight on per 100 parts of heavy carrier materials.Can know that the optimum amount of co-catalyst changes with the difference of the element of making co-catalyst.Make catalytically-active metals and manganese and/or vanadium and make co-catalyst if catalyst comprises cobalt, then cobalt: (manganese+vanadium) mol ratio is preferably at least 12: 1.
Particularly preferred Fischer-Tropsch catalyst is Co/ZrO
2/ SiO
2Catalyst, promptly cobalt is carried on as catalytically-active metals and contains on silica and the zirconic mixture carrier.Before activation, cobalt exists with the form of cobalt oxide.Obtain to have the cobalt of catalytic activity by the reduction-oxidation cobalt.
Used reducing gases can be any gas with reproducibility in principle.But preferred hydrogen-containing gas.
In this explanation, hydrogen-containing gas is the gas that contains hydrogen and nonessential one or more inert gases (as nitrogen).The syngas mixture that contains hydrogen and carbon monoxide is not included in the terminology used here hydrogen-containing gas.But, can know that syngas mixture itself is a kind of reducing gases, can be used for the inventive method equally.If catalyst to be activated comprises iron, then preferably use syngas mixture.
When catalyst activates by contacting with hydrogen-containing gas, in reduction reaction, generated water, and this moisture content flows through catalyst bed with hydrogen-containing gas.Therefore, along with reducing gases increases by water content in the catalyst bed reduction air-flow.Be that right moisture content suppresses reduction reaction, when reducing gases speed and hydrogen content are constant, be obstructed further along the activation of the direction catalyst of reduction air-flow.For this putting should be reduced to Min., preferably in activation process, increase amounts of hydrogen by catalyst bed make the air-flow that leaves catalyst bed after the activation, be that water content in the exit flow remains under the certain level.This level certainly is taken at the catalyst of (again) activation, and can measure by routine test.Usually, work off one's feeling vent one's spleen in water content preferably remain on 6.0 * 10
3Handkerchief (60 millibars) or lower more preferably remains on 5.0 * 10
3Below the handkerchief (50 millibars).
But including the catalyst that contains silica supports can be relatively more responsive to a large amount of steams that exist in (again) activation process.Therefore, carry out (again) when activation if include the catalyst that contains silica supports, quantity of steam preferably is lower than 4.0 * 10 in hydrogeneous the working off one's feeling vent one's spleen
3Handkerchief (millibar) is more preferably less than 3.0 * 10
3Handkerchief (30 millibars).Contain titanium dioxide or zirconic catalyst for some, vapor volume can be higher in hydrogeneous the working off one's feeling vent one's spleen, for example 4.0 * 10
3-1.0 * 10
5In (40-1000 millibar) scope, preferred 4.0 * 10
3-1.0 * 10
4Handkerchief (40-100 millibar).
The method that the amounts of hydrogen of two kinds of increases by catalyst bed arranged, a kind of is gas speed or the content that increases reducing gas in activation process, keeps in the reducing gas hydrogen content in constant level simultaneously; The 2nd, in activation process, increase the hydrogen content in the reducing gases gradually or progressively.Obviously these two kinds of methods of employing also capable of being combined.
In addition, perhaps combine, can reduce the temperature of catalyst bed by the temperature that reduces cooling medium or temporarily stop any temperature rise with water content method during above-mentioned control is worked off one's feeling vent one's spleen.
The Fischer-Tropsch hydrocarbon building-up process of catalysis is suitable for operating in fixed bed, and therefore above-mentioned activation method also is suitable for carrying out fixed-bed operation.But, can recognize that the catalyst that uses also can activate by the inventive method in being different from the catalytic bed of fixed bed.
Activation process itself is suitable for carrying out in the fixed bed of catalyst most.But, in activation process, also be suitable for adopting other catalyst bed, as moving bed.
Activation process is preferably being carried out below 450 ℃, more preferably less than 400 ℃, most preferably is lower than 300 ℃.Activation process is carried out under the temperature more than 150 ℃ usually, and is preferred more than 200 ℃.
The pressure of operating normally 1.0 * 10
5～1.5 * 10
7Handkerchief, (1～150 crust, absolute pressure), preferred 1.0 * 10
5～6.0 * 10
6Handkerchief, (1～60 crust, absolute pressure), more preferably 1.0 * 10
5～2.0 * 10
6Handkerchief, (1～20 crust, absolute pressure).
Gas speed, be that the gas hourly space velocity is generally 100～3000 standard liters/liter/hour, preferred 200～1500 standard liters/liter/hour.
Soak time should be able to be enough to make catalyst reach activation basically usually.Can recognize that length can change during this period of time, depend on catalyst composition, average reaction temperature, gas speed, reducing gases dividing potential drop.Catalyst contacts 0.5～150 hour usually with reducing gases, and preferred 8～120 hours, more preferably 16～96 hours.
According to an embodiment preferred, catalyst contact with reducing gases until at least 25% (weight), preferably at least 50% (weight), more preferably the VIII family metallic compound of at least 80% (weight) is reduced into metallic state.
Can monitor the amount of the VIII family metallic compound in the source of being gone back by the amount of the moisture content accumulated in the measuring process suitably.The known method of those skilled in that art comprises thermogravimetric analysis and temperature-programmed reduction method.
As noted above, temperature, gas speed (GHSV, i.e. gas hourly space velocity) and the content (dividing potential drop) that can change reducing gases is controlled activation process.Can recognize that the optimum mode of selecting to control the activation process of special catalyst by routine test is to grasp for those of ordinary skill.According to the scheme of a typical activation process, temperature, stagnation pressure and total gas speed keep constant, and reducing gases content, preferred hydrogen content rises gradually or progressively, rise to as 85% (volume) or higher from 1%, preferably to 100% (volume).According to another embodiment, temperature continuously or progressively rises, and rises to as 400 ℃ at the most from least 150 ℃, and heating rate is 0.5～5 ℃/minute.
US-A-4 discloses the method for activation Fischer-Tropsch catalyst in 605,676 and US-A-4,670,414, and it comprises continuous several steps: promptly use hydrogen reducing, with the oxygen-containing gas oxidation and with hydrogen reducing with activating catalyst.Institute is all operations between about 100～450 ℃ usually in steps.This activation method is called " ROR processing ".
The very suitable activation step and/or first recovery step of doing in the ROR processing of above-mentioned activation process of the present invention.Therefore, the present invention relates on the other hand by catalyst is contacted the method that activates the Fischer-Tropsch process with following material continuously:
(a) reducing gases;
(b) oxic gas; With
(c) reducing gases,
Wherein step (a) and/or (c), preferred steps (c) operates as previously mentioned.Preferably step (c) original position is carried out at least, and more preferably step (a) to (c) original position is carried out.
Can recognize, be also operating procedure (b) like this, and promptly the oxidizing gas stream direction is opposite with the reaction gas flow direction in the operation.
After operation was finished, Fischer-Tropsch catalyst can carry out reactivation with recycling to this catalyst to the small part inactivation.Activation method of the present invention is suitable for catalyst is carried out reactivation.Therefore, another aspect of the present invention relates to reactivation and fills in the method to the Fischer-Tropsch catalyst of small part inactivation in the bed, promptly catalyst is contacted with reducing gases, wherein reducing gases is opposite with the reaction gas flow direction by the direction of catalyst bed in operation.
Found that the ROR processing also is very suitable for the Fischer-Tropsch catalyst of reactivation to the small part inactivation.Under the situation that is not subjected to the particular theory constraint, when the ROR processing is used for reactivation, seemingly following working.
The first step that ROR handles consists essentially of with hydrogen and removes heavy wax and/or carbon granules (they are deposited on the catalyst granules in operation) and slow reducing catalyst.In the oxidation step subsequently, any carbon granules that still exists on the catalyst is oxidized to carbon dioxide and water, and catalytically-active metals has also produced oxidation.At last, in activation step, the catalyst reduction of oxidation is become activated state, prepare to utilize again by reduction.
The very suitable activation step of doing in the ROR processing of activation method that the present invention is above-mentioned.Therefore, the present invention also relates to reactivation and fill in the method to the Fischer-Tropsch catalyst of small part inactivation in the bed, it comprises following continuous step:
(a) catalyst is contacted with reducing gases, especially hydrogen-containing gas;
(b) catalyst is contacted with oxic gas;
(c) make catalyst contact (being reducing catalyst) with reducing gases, it is characterized in that step (C) is according to above-mentioned activation method operation as one aspect of the invention.
Can recognize, also operating procedure (b) like this, promptly the direction of oxidizing gas stream is opposite with the reaction gas flow direction in the operation.In fact in reactivation to the process of the Fischer-Tropsch catalyst of small part inactivation, if for example behind the oxidation carbon granules, produced a large amount of moisture content, can preferably operate like this.The existence of a large amount of moisture content for example can be induced the formation of metallic carrier compound.Therefore, according to an embodiment, the feature of above-mentioned ROR method is that further oxic gas is opposite with the direction of reaction gas flow by the direction of catalyst bed in step (b) operation.According to an embodiment of the present invention, carry out oxidation when step, water content remains on as discussed above in the scope in working off one's feeling vent one's spleen, but also can preferably be higher or lower than the amount of this scope.
Also can carry out step (a) so in theory, promptly make the direction of reduction air-flow opposite in the operation with the reaction gas flow direction.But, as the Fischer-Tropsch of reactivation to the small part inactivation
Step (a) in the ROR method of catalyst, it mainly comprises removes carbon granules and heavy wax, if such operating procedure (a) then can not produce substantial improvement.
All steps are preferably carried out in 150～400 ℃ of scopes, more preferably 200～300 ℃.
The condition of describing in above mentioned two United States Patent (USP)s is applicable to step (a) and (b).Preferred hydrogen is done the reducing gases in the step (a), with the oxygenous oxic gas of doing in the step (b).Suitable oxygenous example is a diluent air, the air of promptly having used as the inert gas dilution of nitrogen.Preferably contain 0.1～10% (volume), the more preferably oxygen of 0.2～5% (volume) in oxygenous.
Oxygen content preferably is controlled at is used as controlling oxidation a kind of mode in step in the above-mentioned scope.The operating condition of step (b) is preferably identical with listed scope in above-mentioned activation (reduction) method.Also can use higher oxygenous of oxygen content in theory, as air.Those skilled in that art can recognize, in order to control oxidation reaction, and can corresponding adjustment reaction condition.
The operating condition of step (a) is preferably with step (c) during the ROR that lists above handles, promptly the operating condition of activation (reduction) process is identical.But can recognize that if ROR handles when being used for reactivation to the catalyst of small part inactivation, most VII family metal has been metallic state in the catalyst.But, preferably catalyst is contacted 0.5～150 hour with reducing gases, more preferably 8～120 hours, most preferably 16～96 hours.In addition, according to an embodiment preferred, when reactivation during to the catalyst of small part inactivation, the maintenance in the step (a) that ROR handles of hydrogen content and other operating condition (as temperature) is constant in the hydrogen-containing gas.The hydrogen partial pressure of step in the processing (a) preferably is lower than 1.5 * 10
6Handkerchief (15 crust, absolute pressure) is more preferably less than 1.0 * 10
6Handkerchief (10 crust, absolute pressure).
By following examples the present invention is further specified.
Embodiment 1
Catalyst system therefor is 1.7 millimeters trilobe Fischer-Tropsch catalysts, based on the catalytic amount of complete oxidation, wherein comprises 23% (weight) Co, 10% (weight) ZrO
2And the SiO of 56% (weight)
2This experiment is carried out in the individual layer basket Chinese style device of two reactors that series connection is housed.Long 4 meters of each reactor.The volume of each catalyst bed is 1950 milliliters.
Reverse flow activates following operation.Reducing gases is by 250 ℃ and 4.0 * 10
5Catalyst bed under the handkerchief (4 crust), its flow direction is opposite with airflow direction in the standard operation.Reducing gases be nitrogen/hydrogen mixture and in activation process hydrogen partial pressure rise, make that water content is below 5000PPM (volume) in the exit gas.Maximum hydrogen content is 75% (volume) in the reduction air-flow.Gas hour space flow speed (GHSV) is 600 standard liters/liter/hour, and the whole recovery time is 48 hours.Actual conditions is listed in table 1.
Contain Co/H subsequently
2The activating catalyst that obtains by said method of gas.Reaction condition and operate after 50 hours the table of measuring 3 that the results are shown in operate after 50 hours and is seen Fig. 1 along the temperature curve of catalyst bed mensuration.
Comparative example 1
The identical catalyst that adopts among activation and the embodiment 1 is promptly by allowing reducing gases pass through catalyst bed (normal stream activation) with the direction identical with airflow direction in the standard operation.Condition is listed in table 2.
Contain Co/H
2Gas subsequently by as the activating catalyst that obtains of above-mentioned method.Used condition and operate after 50 hours the table of measuring 3 that the results are shown in operate after 50 hours and is seen Fig. 1 along the temperature curve of catalyst bed mensuration.
Table 1 reverse flow activation
| Time (hour) | N 2/H 2Total air flow (the standard liter/hour) | Hydrogen content in the reducing gases (volume %) | The middle water content (ppm volume) of working off one's feeling vent one's spleen |
| 0.0 | 2010 | 0.5 | |
| 1.0 | 2020 | 1.0 | 926 |
| 2.0 | 2020 | 1.0 | 3878 |
| 4.0 | 2020 | 1.5 | 4331 |
| 6.0 | 2040 | 2.0 | 4123 |
| 8.0 | 2000 | 8.0 | 4746 |
| 10.0 | 2200 | 40.0 | 3707 |
| 25.0 | 2400 | 75.0 | 1973 |
| 32.5 | 2400 | 75.0 | 1037 |
| 48.0 | 2400 | 75.0 | 670 |
The activation of table 2 normal stream
| Time (hour) | N 2/H 2Total air flow (the standard liter/hour) | Hydrogen content in the reducing gases (volume %) | The middle water content (ppm volume) of working off one's feeling vent one's spleen |
| 0.0 | 2010 | 0.5 | |
| 1.0 | 2020 | 1.0 | 946 |
| 2.0 | 2020 | 1.0 | 2886 |
| 4.0 | 2030 | 1.5 | 3076 |
| 6.0 | 2000 | 4.0 | 3978 |
| 8.0 | 2000 | 16.0 | 3356 |
| 10.0 | 2200 | 40.0 | 3162 |
| 24.0 | 2200 | 75.0 | 1795 |
| 32.0 | 2200 | 75.0 | 909 |
| 48.0 | 2200 | 75.0 | 558 |
Table 3
Fischer-Tropsch is synthetic
| Embodiment 1 | Comparative example 1 | ||
| The gas hourly space velocity (the standard liter/liter/hour) | H 2 | 479 | 466 |
| CO | 434 | 435 | |
| Inert gas | 218 | 242 | |
| Total amount | 1131 | 1143 | |
| Inlet pressure (10 6Handkerchief/crust) | 3.78/37.8 | 3.83/38.3 | |
| Inlet H 2/ CO is than (volume/volume) | 1.10 | 1.07 | |
| Liquid velocity (mm/second) | 1.5 | 1.5 | |
| Coolant temperature (℃) | 210 | 209 | |
| The weight average bed tempertaure (℃) | 213 | 216 | |
| Space-time yield (grams per liter/hour) | 105.1 | 101.4 | |
| C5 +Selectivity (weight %) | 92.2 | 89.4 | |
As can be seen from Table 3, reverse flow operation according to the present invention produces the better catalyst of performance.At lower weight average bed tempertaure (WABT), i.e. the C1 of the catalyst by adverse current activation
+Productive rate and C5
+Selectivity all is higher than the catalyst by the standard activation.C1
+Productive rate is meant space-time yield (STY), i.e. the gram number of the hydrocarbon with two or more carbon atoms that per hour produces of every liter of catalyst.
List the temperature curve that the operation of reverse flow activating catalyst and normal stream activating catalyst was measured along two 4 meters long reactor after 50 hours among Fig. 1.Ordinate is illustrated in the cooling agent and the interior temperature difference of reactor in the hydrocarbon synthesis reaction, and abscissa is represented the distance from a last reactor head.
As seen from Figure 1, temperature curve ratio along the reactor that contains the adverse current activating catalyst (RAC reactor) is milder along the temperature curve of the reactor (NAC reactor) of the catalyst that contains the standard activation, and this shows that the temperature in the RAC reactor is more constant than the temperature in the NAC reactor in the hydrocarbon synthesis reaction process.This shows along the activity of such catalysts of the adverse current activation of whole reactor more constant conversely, and transform level also fluctuates less like this.Can see that from table 3 this produces favourable influence to total conversion ratio: air factor was higher than the final space-time yield of reacting when the reaction in the RAC reactor was final in the RAC reactor, and C5
+Selection rate is also higher.
Claims (10)
1. an activation is filled in the method for the Fischer-Tropsch catalyst in the bed, even catalyst contact with reducing gases below 500 ℃ before operation, to pass through the direction of catalyst bed opposite with the reaction gas flow direction for reducing gases in it is characterized in that operating.
2. according to the process of claim 1 wherein that reducing gases is a hydrogen-containing gas.
3. according to the method for claim 2, wherein reducing gases is the mixture of nitrogen and hydrogen.
4. according to the method for claim 2 or 3, wherein increased in the activation process by the amounts of hydrogen of catalyst bed, leave after the activation that water content is no more than 6.0 * 10 in the air-flow of catalyst bed
3Handkerchief (60 millibars).
5. according to each method in the aforementioned claim, wherein Fischer-Tropsch catalyst comprises cobalt.
6. a reactivation is filled in the method to the Fischer-Tropsch catalyst of small part inactivation in the bed, even catalyst is contacting below 500 ℃ with reducing gases, reducing gases is opposite with the reaction gas flow direction by the direction of catalyst bed in it is characterized in that operating.
7. activation Fischer-Tropsch catalyst or reactivation are to the method for the Fischer-Tropsch catalyst of small part inactivation, and it comprises following continuous several steps:
(a) catalyst contacts with reducing gases;
(b) catalyst contacts with oxic gas;
(c) catalyst contacts with reducing gases;
It is characterized in that step (c) operates according to each method in the claim 1 to 6.
8. according to the method for claim 7, wherein the reducing gases of using in the step (a) is a hydrogen-containing gas.
9. according to the method for claim 7 or 8, wherein the oxic gas of using in the step (b) is oxygenous.
10. each method in the aforementioned claim, wherein activation or reactivation process original position are carried out.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94203562 | 1994-12-07 | ||
| EP94203562.7 | 1994-12-07 |
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| Publication Number | Publication Date |
|---|---|
| CN1132665A CN1132665A (en) | 1996-10-09 |
| CN1079701C true CN1079701C (en) | 2002-02-27 |
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|---|---|
| CN (1) | CN1079701C (en) |
| AU (1) | AU688631B2 (en) |
| CA (1) | CA2164462A1 (en) |
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| US6486220B1 (en) | 1999-11-17 | 2002-11-26 | Conoco Inc. | Regeneration procedure for Fischer-Tropsch catalyst |
| US6869978B2 (en) | 1999-11-17 | 2005-03-22 | Conocophillips Company | Pressure swing catalyst regeneration procedure for Fischer-Tropsch catalyst |
| US7045554B2 (en) | 2003-09-03 | 2006-05-16 | Conocophillips Company | Method for improved Fischer-Tropsch catalyst stability and higher stable syngas conversion |
| US8809215B2 (en) | 2007-05-11 | 2014-08-19 | Sasol Technology (Proprietary) Limited | Catalysts |
| CN106001597B (en) * | 2016-07-08 | 2018-03-20 | 武汉工程大学 | The recovery method of copper post in a kind of elemental analyser |
| CN108816295A (en) * | 2018-06-09 | 2018-11-16 | 濮阳市联众兴业化工有限公司 | A kind of high-nickel catalyst activation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605679A (en) * | 1981-10-13 | 1986-08-12 | Chevron Research Company | Activated cobalt catalyst and synthesis gas conversion using same |
| US4605460A (en) * | 1983-10-03 | 1986-08-12 | W. R. Grace & Co., Cryovac Div. | Method of laminating high barrier shrink film |
| EP0533228A1 (en) * | 1991-08-20 | 1993-03-24 | Shell Internationale Researchmaatschappij B.V. | Process for the activation of a catalyst |
| EP0533227A1 (en) * | 1991-08-20 | 1993-03-24 | Shell Internationale Researchmaatschappij B.V. | Process for the activation of a Fischer-Tropsch catalyst and the activated catalyst |
| CN1070594A (en) * | 1991-07-02 | 1993-04-07 | 英国石油有限公司 | Catalyst treatment |
| US5292705A (en) * | 1992-09-24 | 1994-03-08 | Exxon Research & Engineering Co. | Activation of hydrocarbon synthesis catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2258826A (en) * | 1991-08-20 | 1993-02-24 | Shell Int Research | Process for the activation of a catalyst |
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1995
- 1995-12-04 AU AU40216/95A patent/AU688631B2/en not_active Ceased
- 1995-12-05 ZA ZA9510296A patent/ZA9510296B/en unknown
- 1995-12-05 CN CN95120515A patent/CN1079701C/en not_active Expired - Fee Related
- 1995-12-05 CA CA 2164462 patent/CA2164462A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605679A (en) * | 1981-10-13 | 1986-08-12 | Chevron Research Company | Activated cobalt catalyst and synthesis gas conversion using same |
| US4605460A (en) * | 1983-10-03 | 1986-08-12 | W. R. Grace & Co., Cryovac Div. | Method of laminating high barrier shrink film |
| CN1070594A (en) * | 1991-07-02 | 1993-04-07 | 英国石油有限公司 | Catalyst treatment |
| EP0533228A1 (en) * | 1991-08-20 | 1993-03-24 | Shell Internationale Researchmaatschappij B.V. | Process for the activation of a catalyst |
| EP0533227A1 (en) * | 1991-08-20 | 1993-03-24 | Shell Internationale Researchmaatschappij B.V. | Process for the activation of a Fischer-Tropsch catalyst and the activated catalyst |
| US5292705A (en) * | 1992-09-24 | 1994-03-08 | Exxon Research & Engineering Co. | Activation of hydrocarbon synthesis catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2164462A1 (en) | 1996-06-08 |
| ZA9510296B (en) | 1996-06-11 |
| AU688631B2 (en) | 1998-03-12 |
| AU4021695A (en) | 1996-06-13 |
| CN1132665A (en) | 1996-10-09 |
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