CN1803281A - Ferriferous catalyst containing adjuvant used in fischer tropsch process and its production method - Google Patents
Ferriferous catalyst containing adjuvant used in fischer tropsch process and its production method Download PDFInfo
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- CN1803281A CN1803281A CN 200610017390 CN200610017390A CN1803281A CN 1803281 A CN1803281 A CN 1803281A CN 200610017390 CN200610017390 CN 200610017390 CN 200610017390 A CN200610017390 A CN 200610017390A CN 1803281 A CN1803281 A CN 1803281A
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Abstract
The invention discloses a catalyst with Runny iron adjuvant, which is composed of 72.9 percent iron, 0-6.1 percent titanium, 0-8.2 percent manganese, 0-4.9 percent potassium and aluminum. The making method comprises the following steps: mixing the block-shaped or powder iron, aluminum and or titanium, manganese metal or metal oxide composition; heating the mixture into evenness-phase alloy; quenching the mixture into atmospheric temperature to produce the pioneer body of catalytic alloy; grinding; disposing the alloy particle through alkali solution; filtering most of aluminum; soaking the alloy in the alcohol with potassium; drying to make the potassium on the catalyst with Runny iron adjuvant; proceeding activating disposal through hydrogen or synthetic gas in the Fetus synthetic reaction.
Description
Technical field
The present invention relates to a kind of Fe-series catalyst and method for making thereof, contain auxiliary agent Renyi iron catalyst and method for making thereof especially for fischer tropsch process.Catalyst of the present invention is improving catalyst Fischer-Tropsch synthesis activity, middle bottoms product productive rate, all there is remarkable improvement the advantage aspect of suitable slurry attitude bed catalytic reactors such as catalyst abrasion resistance and catalyst sedimentation separative efficiency, and it has the good performance that is applied to industrialization Fischer-Tropsch building-up process.
Background technology
Fischer-Tropsch catalysis building-up process is well-knownly will contain CO, H
2It is the effective way that main synthesis gas is converted into industrial chemicals and liquid hydrocarbon product.Catalyst at this reaction process exploitation has multiple metal system, comprises the dissimilar catalyst based on components such as iron, nickel, cobalt, rhodium, rutheniums.Wherein Fe-series catalyst is again the catalyst that the low cost of welcoming the most and high-performance are applicable to the low hydrogen-carbon ratio synthesis gas, the most extensive as the application study of precipitated iron catalyst in this Fischer-tropsch process, catalytic activity and desired product selectivity are all than higher, but but very easily broken in course of reaction, form micron catalyst fine particles of following (nanometer); The granularity that causes under this because physics and the chemical action is demoted and is amplified the separating difficulty that field investigation has been brought catalyst granules and heavy hydrocarbon product wax to laboratory and even industry, makes numerous corresponding Fischer-tropsch process rest on laboratory scale and can't amplify.Under this background, some targetedly the new technology patent arise at the historic moment, basic Renyi iron catalyst has experienced a large amount of laboratories and has amplified checking, as U.S. Pat 6265451 and US6277895 as a kind of Fischer-Tropsch synthetic iron-based catalyst of novelty.But this basic Renyi iron catalyst is still treated further improvement in many aspects, comprises catalyst activity and desired product selectivity.
Summary of the invention
The object of the present invention is to provide a kind of be used for fischer tropsch process contain auxiliary agent Renyi iron catalyst, it can overcome the deficiency of prior art, can improve catalyst Fischer-Tropsch synthesis activity effectively, middle bottoms product productive rate, catalyst abrasion resistance and catalyst sedimentation separative efficiency have the good performance that is applied to industrialization Fischer-Tropsch building-up process.
Another object of the present invention is to provide a kind of preparation method who contains auxiliary agent Renyi iron catalyst who is used for fischer tropsch process.
Provided by the invention have specific composition and be applied to through the Fischer-Tropsch synthetic reaction by H
2Contain auxiliary agent Renyi iron catalyst with the CO unstripped gas generates purpose liquid hydrocarbon product process, with the metallic element weight that contains auxiliary agent Renyi iron catalyst is benchmark, the present invention contains iron, the titanium of 0-6.1 (weight) %, the manganese of 0-8.2 (weight) % and the potassium of 0-4.9 (weight) % that auxiliary agent Renyi iron catalyst contains 72.9-90.8 (weight) %, and all the other then are aluminium.This specific area that contains auxiliary agent Renyi iron catalyst is at 20-80m
2/ g scope, 45-65m more fortunately
2/ g scope, size distribution be at the 10-10000 mu m range, more fortunately the 30-200 mu m range.
Contain auxiliary agent Renyi iron catalyst preferably and comprise 86.3-90.4 (weight) % iron, 2.4-9.8 (weight) % aluminium, 1.8-3.2 (weight) % titanium, 1.5-6 (weight) % manganese, 0.8-1.5 (weight) % potassium, specific area is 45-65m
2/ g, granularity is 30-200 μ m.
The method for preparing this catalyst comprises the steps:
1) iron, aluminium and/or titanium, manganese or their oxide with bulk or powdery is mixed together, and this mixture of heating and melting forms the homogeneous phase alloy under inert atmosphere in heater;
2) cool off above-mentioned gained alloy fast to room temperature, be generally 15-30 ℃, form the catalyst alloy presoma;
3) Mechanical Crushing gained catalyst alloy presoma is to the alloying pellet of the particle size range of 100-10000 μ m, and this alloy granular precursor contains 35-55 (weight) % iron, 40-60 (weight) % aluminium, 0-10 (weight) % titanium and 1-15 (weight) % manganese;
4) gained catalyst alloy granular precursor and concentration range are at the aqueous slkali of 10-50%, for example NaOH or potassium hydroxide carry out strong exothermal reaction, particularly, alloying pellet is with after alkali lye contacts fully, temperature need keep 50-150 minute at 50-90 ℃, so the most of metallic aluminium in the alloying pellet can dissolve through reaction, thereafter spend deionised water, make that alloying pellet surface liquid pH value is 7, with absolute ethyl alcohol water is replaced at last, make and contain auxiliary agent Renyi iron catalyst main body particle, and be stored in and treat next step processing in the absolute ethyl alcohol.
Described catalyst alloy presoma comprises 38 (weight) % and iron, the aluminium of 58 (weight) %, the titanium of manganese and 2 (weight) % of 2 (weight) %.
Can also support potassium in above-mentioned containing on the auxiliary agent Renyi iron catalyst main body of obtaining.Concrete steps are: use a kind of alcoholic solution dipping gained of potassium to contain auxiliary agent Renyi iron catalyst main body, whole steps under vacuum and temperature programming evaporate all liq solvent and finish, obtain to contain 0.1-4.9 (weight) % the potassium loading contain auxiliary agent Renyi iron catalyst.
The solvent evaporation that described potassium supports process is to finish under 40-80 ℃ temperature and 100-500mmHg vacuum.
It is by being that the alcoholic solution dipping of the potassium compound of 0.1-0.5N contains auxiliary agent Renyi iron catalyst main body and realizes with a kind of concentration that described potassium supports.
The alcoholic solution of described potassium is selected from following several solns: methanol-hydrogen potassium oxide solution, ethanol-potassium hydroxide solution, ethanol-solution of potassium carbonate.
5) will contain auxiliary agent Renyi iron catalyst activates.Described activation is included in and is applied to carry out the hydrogen treat activation in fixed bed reactors, perhaps hydrogen or synthesis gas activation on the throne in slurry bed ft synthetic reactor before the Fischer-Tropsch synthesis.
In the preparation process that contains auxiliary agent Renyi iron catalyst: at first with the metal derby or the metal-oxide powder of iron block or powder and required nonferrous metal such as aluminium and titanium, manganese, evenly mix with the non-ferrous components ratio of 30-70 (weight) % in 20-80 (weight) % iron, typical mixed proportion scope is counted by weight percentage: the manganese (or manganese sesquioxide managnic oxide) of the iron of 35-55%, the aluminium of 40-60%, 1-15%, the titanium (or titanium dioxide) of 0-10%.To forming a uniform molten state alloy, the method quenching of then adopting water-quenching is generally 15-30 ℃ to room temperature to this mixture through heating and melting.Obtain the catalyst alloy presoma of granularity through fragmentation at 10-10000 μ m.The metallic element of catalyst alloy presoma is distributed as: 35-55 (weight) % iron, 40-60 (weight) % aluminium, 0-10 (weight) % titanium and 1-15 (weight) % manganese.This catalyst alloy presoma then through the NaOH of 10-50% or the KOH aqueous solution 50-90 ℃ down and time enough for example under 20-150 minute the reagentia, most aluminium suction filtration is gone out, be left promptly to contain substantially auxiliary agent Renyi iron catalyst.
Gained can also be contained auxiliary agent Renyi iron catalyst and transfer in the alcoholic solution of suitable potassium and flood, then alcoholic solvent be evaporated, form contain 0.1-1.5 (weight) % potassium loading contain auxiliary agent Renyi iron catalyst.The alcoholic solution of suitable potassium includes but not limited to: methanol-hydrogen potassium oxide, ethanol-potassium hydroxide, potash-water-alcohol etc.
Gained contains auxiliary agent Renyi iron catalyst and need activate before use.Can adopt in fixed bed, finish under the condition such as 0.05-1.0NL/gcat/h hydrogen flowing quantity, 300-350 ℃ temperature, 2-12 hour, and then for example atoleine or ethanol are transferred in the reactor stand-by via suitable reaction medium.Equally, this contain auxiliary agent Renyi iron catalyst also can be at first with reaction medium for example atoleine mix to form slurries and be transferred in the three-phase fischer-tropsch reactor directly and under conditions such as 0.3-3.0NL/gcat/h flow, 300-350 ℃ temperature, 3-48 hour, finish activation process with hydrogen; Also can under such condition, finish: 240-260 ℃ of temperature, 0.5-2.0NL/gcat/h synthesis gas (H with synthesis gas
2/ CO=1.0) flow was handled 6-24 hour down.Both pressure are all at 0.3-0.5MPa.This contains auxiliary agent Renyi iron catalyst can be effectively applied to H
2With the process of CO synthesis gas through products such as Fischer-Tropsch reaction generation hydro carbons.
What finally obtain contains auxiliary agent Renyi iron catalyst grain graininess in the 10-10000 mu m range, wherein the particle of granularity in the 1000-10000 mu m range can be used for fixing bed bioreactor, and granularity then is used for paste state bed reactor at the granule of 20-200 mu m range.
The present invention contains auxiliary agent Renyi iron catalyst whole process of preparation can specifically be divided into following a few part:
1. contain the preparation of auxiliary agent Renyi iron catalyst alloy presoma
The iron and the nonferrous metal component of bulk or powdery are pressed 35-55 (weight) % iron, and 40-60 (weight) % aluminium and 5-15 (weight) % titanium, manganese metal oxide powder form mixture.In a suitable device, as arc-induced graphite high temperature furnace, the heating of metal mixture is quickly cooled to room temperature thereafter to molten state alloy uniformly, generally is cooled to 15-30 ℃ being less than in time of 10 seconds.Obtain alloy granularity at the 10-10000 mu m range with the Mechanical Crushing method afterwards.
2. contain the preparation of auxiliary agent Renyi iron catalyst main body
The process that contains auxiliary agent Renyi iron catalyst by this catalyst alloy presoma preparation needs to finish in atmosphere of inert gases, concrete operations are as follows: be equipped with NaOH or the KOH solution (10-50% concentration) of putting into q.s in the container that stirs in advance one, heated solution is to design temperature (30-95 ℃), progressively join catalyst alloy granular precursor (10-10000 μ m granularity) in the solution then, treat that this alloying pellet adds the back that finishes and keeps being reflected under the controlled condition 20-150 minute, so that the most of aluminium in the alloy is gone out by alkali lye effect suction filtration.Then spend this alloying pellet that deionised water was handled, near 7, then water is replaced, and the auxiliary agent Renyi iron catalyst main body that contains that gained is basic is stored in the absolute ethyl alcohol with absolute ethyl alcohol until alloying pellet surface solution pH value.
3. contain supporting of potassium on the auxiliary agent Renyi iron catalyst main body
What obtain contained auxiliary agent Renyi iron catalyst main body before activation and using, need auxiliary agent potassium (potassium oxide) dipping to be got on: the alcoholic solution that at first will prepare a potassium by following operation, the for example carbonic acid of potassium or salpeter solution, wherein potassium content is with respect to the part by weight of iron content in the catalyst and decide, i.e. 0.5-4.9 potassium: 100 iron.The alcoholic solution that will contain auxiliary agent Renyi iron catalyst main body particle then and prepare mixes puts into rotary evaporator, under certain condition, as: 40-80 ℃ of temperature, the 100-500mmHg decompression, in 30-180 minute alcohol waited all solution evaporations, obtain dry support auxiliary agent potassium contain auxiliary agent Renyi iron catalyst.Can put into container with the pure and mild auxiliary agent Renyi iron catalyst main body that contains of mixing earlier in the concrete evaporation process, after alcoholic solvent to be evaporated finishes this catalyst granules bone dry, slowly import the alcoholic solution that contains potassium again, carry out double evaporation-cooling, obtain more satisfactory potassium loading.
4. contain the activation of auxiliary agent Renyi iron catalyst
Through containing auxiliary agent Renyi iron catalyst after the vacuum drying, before being applied to fischer-tropsch reactor, can activate by following a kind of approach among both.
Gained is contained in auxiliary agent Renyi iron catalyst transfer of granules to fixed bed reactors, after the hydrogen treat activation, again be transferred in the fischer-tropsch reactor, wherein transfer process needs the protection of inert gas, activation condition in fixed bed is: the 0.05-1.0NL/gcat/h hydrogen flowing quantity, 300-350 ℃ of temperature, 2-12 hour processing time; Perhaps be 240-260 ℃ of temperature, 0.5-2.0NL/gcat/h synthesis gas (H
2/ CO=1.0) flow was handled 6-24 hour down.Both pressure are all at 0.3-0.5MPa.
The dried auxiliary agent Renyi iron catalyst particle that contains, also can be by with a certain amount of reaction medium atoleine formation slurry for example, be transferred to activation on the throne in the slurry attitude phase fischer-tropsch reactor then, used condition is: the 0.3-3.0NL/gcat/h hydrogen flowing quantity, 300-350 ℃ of temperature handled 3-48 hour or 240-260 ℃ of temperature, 0.5-2.0NL/gcat/h synthesis gas (H
2/ CO=1.0) flow was handled 6-24 hour down.
Contain the application of auxiliary agent Renyi iron catalyst in Fischer-Tropsch synthesis
The auxiliary agent Renyi iron catalyst that contains of the present invention is to containing CO and H
2Unstripped gas is extremely effective through the process that the Fischer-Tropsch synthetic reaction generates required hydrocarbon product, and it is synthetic to be specially adapted to starch attitude phase reactor Fischer-Tropsch.Suitable reaction condition is: H
2With the CO mol ratio be 0.5-5: 1, catalyst weight concentration is that 5-40% is (with respect to reaction medium, atoleine for example), fixed bed reactors are used the 1-10mm grain graininess, slurry attitude phase reactor is adopted the granularity of 20-200 μ m, reaction pressure is 1.0-3.0MPa, and the gas space velocity flow is 0.5-5.0NL/gcat/h.To carry out Separation of Solid and Liquid by the constant temperature sedimentation behind purpose product liquid hydrocarbon and the catalyst system therefor particulate emission.
Provided by the inventionly contain titanium, manganese and the potassium etc. that auxiliary agent Renyi iron catalyst mainly comprises iron and amount of auxiliary.With the metallic element weight that contains auxiliary agent Renyi iron catalyst is benchmark, and this contains auxiliary agent Renyi iron catalyst and contains 72.9-90.8 (weight) % iron, 0-6.1 (weight) % titanium, 0-8.2 (weight) % manganese and 0-4.9 (weight) % potassium, and all the other then are aluminium.This specific area that contains auxiliary agent Renyi iron catalyst is at 20-80m
2/ g scope, 45-65m more fortunately
2/ g, size distribution is at 10-10000 μ m, 30-200 μ m more fortunately.This contains auxiliary agent Renyi iron catalyst and has good practical physical intensity and advantages of high catalytic activity and higher by H
2Generate the selectivity that desired product is mainly liquid fuel with the CO unstripped gas.This typical precipitated iron catalyst that contains the activity of auxiliary agent Renyi iron catalyst and current extensive employing is suitable, and all good on the diesel product selectivity than precipitated iron and molten iron, this contains, and auxiliary agent Renyi iron catalyst can be applied to fixed bed or the paste state bed reactor Fischer-Tropsch synthesizes to come production purpose hydrocarbon product.The rich alpha-olefin of its gained hydrocarbon liquids product can be as the high industrial chemicals of economic worth after downstream separation technology.
The present invention contains auxiliary agent Renyi iron catalyst and makes by improved method, that is, iron, aluminium and/or the titanium of bulk or powdery and the metal or the oxide of manganese are mixed, add hot mixt to molten state and after evenly forming alloy liquid, be quickly cooled to room temperature state, for example water quenching etc.; Then with the granularity of gained alloy sample Mechanical Crushing to 100-10000 μ m., alloy is handled with suitable aqueous slkali such as NaOH or KOH thereafter, strong exothermal reaction takes place after the heavy metallic aluminium of alloy removed by most of suction filtration, form the basic auxiliary agent Renyi ferrum-based catalyst body that contains.By alcoholic solution dipping, finally support the potassium of 0.1-3.0 (weight) % after this ferrum-based catalyst with potassium.This contain auxiliary agent Renyi iron catalyst can be in fixed bed reactors direct high-temperature activation, perhaps activation on the throne in paste state bed reactor.The gained catalyst possesses by H
2Setting out with the CO unstripped gas generates the greater activity of multiple desirable hydrocarbon product through Fischer-Tropsch reaction, good abrasion resistance in the operation.Because of the higher characteristics of density of catalyst system therefor, separate with heavy product through sedimentation easily simultaneously.Therefore, the fischer-tropsch synthesis process of the suitable especially paste state bed reactor of this catalyst.
The auxiliary agent Renyi iron catalyst that contains of the present invention is compared with fused iron catalyst with traditional precipitated iron and is had a lot of advantages, also is the remarkable improvement to existing basic Renyi iron catalyst.These advantages show the preparation method of simplification, promptly adopt raw materials such as metal or oxide, and through fusion, cool off, be crushed to required particle size, final catalyst is formed and the catalyst precursor of granularity and controlled easily; Simultaneously, owing to adopt improved method that potassium promoter is supported on the catalyst, selection of catalysts and service life have significantly been improved.Catalyst of the present invention is by after fixed bed or the effective activation on the throne of slurry attitude bed, under the industrial reaction condition, especially can reach higher synthesis gas conversion ratio (CO conversion ratio＞80%) in the paste state bed reactor, enough long stabilizing active, good middle distillate fuel and alpha-olefin selectivity of product.Simultaneously, the good resistance abrasiveness of catalyst of the present invention makes the separation problem of Fischer-Tropsch synthetic heavy product and solid phase be readily solved.
The specific embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with embodiment.
Embodiment 1
1. at first iron, aluminum metal piece were mixed by weight 42: 58, in the arc-induced graphite furnace and with under the argon shield, be heated to molten state, and form even liquid alloy.Afterwards the molten state alloy is quickly transferred in the water quenching to room temperature (15-30 ℃), Mechanical Crushing obtains the catalyst alloy granular precursor of 100-3000 μ m granularity.
2. the 25%NaOH solution of placing 2 liters is in a multinecked flask, and water-bath is heated to 55 ℃, slowly to wherein adding alloying pellet 100 grams that step 1 obtains.Add this alloying pellet back that finishes and keep that reaction condition is constant to continue 90 minutes, with the most of metallic aluminium dissolving in this alloy.The remaining solid particle of filtering reaction spends this particle of deionised water to pH value and reaches 7 then, and after replacing the water that retains with absolute ethyl alcohol, catalyst granules is stored in the ethanol.The Renyi iron catalyst that obtains after this step has 45m
2The granularity of the specific area of/g and 30-200 μ m; Consist of: 72.9 (weight) % iron, 27.1 (weight) % aluminium.
3. gained Renyi iron catalyst is transferred in the fixed bed reactors, activation is 8 hours under 0.7NL/gcat/h hydrogen flowing quantity and 350 ℃ of temperature, subsequently under the high-purity nitrogen gas shiled with the catalyst activated transfer of granules in slurry attitude phase reaction medium.Be applied to the CO+H on this catalyst
2Slurry attitude phase Fischer-Tropsch synthesis condition is: the catalyst grain size of 0.044-0.074mm, and with respect to 15 (weight) % catalyst concn of reaction medium, 0.7: 1 H
2With the CO mol ratio, 260 ℃ reaction temperature and the reaction pressure of 2.5MPa.The results are shown in Table 1 for the activity rating of precipitated iron catalyst under similar reaction condition of this Renyi iron catalyst and contrast.
Embodiment 2
At first with metallic iron, metallic aluminium, titania powder and manganese sesquioxide managnic oxide powder by weight 38: 58: 2: 2 mix, and are heated to molten state in arc-induced graphite high temperature furnace He under the argon shield, and stirring makes it even.Thereafter gained iron-aluminium-titanium-manganese liquid alloy is quickly transferred in the water, quenching is to room temperature (15-30 ℃), and Mechanical Crushing obtains the catalyst alloy granular precursor of 100-3000 μ m granularity.
2. the 25%NaOH solution of placing 2 liters in advance is in three-neck flask, and water-bath is heated to 75 ℃, slowly to wherein adding the alloying pellet that step 1 obtains.Add this alloying pellet back that finishes and keep that reaction condition is constant to continue 90 minutes, so that the most of metallic aluminium dissolving suction filtration in the alloy is fallen.Spend alloying pellet to the pH value that deionised water handled then and reach 7, and temporarily be stored in the ethanol after replacing water with absolute ethyl alcohol.Gained contains auxiliary agent Renyi iron catalyst and has 56m
2The granularity of the specific area of/g and 30-200 μ m; Consist of: 86.9 (weight) % iron, 6.8 (weight) % aluminium, 1.5 (weight) % manganese, 1.8 (weight) % titanium.
3. gained being contained auxiliary agent Renyi iron catalyst is transferred in the fixed bed reactors; under 0.7NL/gcat/h hydrogen flowing quantity and 350 ℃ of temperature, activate 8 hours, under highly purified nitrogen protection, the catalyst activated transfer of granules is estimated in slurry attitude phase reaction medium subsequently.Be applied to the CO+H on this catalyst
2Slurry attitude phase Fischer-Tropsch synthesis condition is: the catalyst grain size of 0.044-0.074mm, and with respect to 15 weight % catalyst concns of reaction medium, 0.7: 1 H
2, CO mol ratio, 260 ℃ reaction temperature and the reaction pressure of 2.5MPa.This contains the activity rating of precipitated iron catalyst under similar reaction condition of auxiliary agent Renyi iron catalyst and contrast, and the results are shown in Table 1.
After the catalyst activity evaluation finished, the remaining slurries that contain auxiliary agent Renyi iron catalyst and product wax were used to carry out 60 minutes gravity settling separation test under different temperatures in the reactor, and concrete separating resulting sees table 2 for details.
Embodiment 3
At first with iron, aluminum metal piece, titanium dioxide and manganese carbonate powder by weight 38: 58: 2: 2 mix, and are heated to molten state in the arc-induced graphite furnace He under the argon shield, and stirring makes it even.Thereafter gained iron-aluminium-titanium-manganese liquid alloy is quickly transferred into that quenching is to room temperature (15-30 ℃) in the water, Mechanical Crushing obtains the catalyst alloy granular precursor of 100-3000 μ m granularity.
2. the 25%NaOH solution of placing 2 liters in advance is in a three-neck flask, and water-bath is heated to 75 ℃, slowly to wherein adding the alloying pellet that step 1 obtains.Add this alloying pellet back that finishes and keep that reaction condition is constant to continue 90 minutes, through with this alloy of alkaline reaction in most of metallic aluminium dissolved.It is approaching or reach 7 to pH value to spend the particle that filters out after the deionised water reaction, and replaces the water that retains with absolute ethyl alcohol and obtain containing auxiliary agent Renyi iron catalyst main body particle and be stored in the absolute ethyl alcohol.
3. at first prepare the methanol solution of potassium (selecting potash for use), and obtain containing auxiliary agent Renyi iron catalyst main body particle with step 2 and mix, concrete proportioning is that the weight ratio according to iron in potassium and the catalyst is 2: 100.Temperature programming will pure and mild a spot of aqueous solvent evaporation under 200mmHg decompression, 60 ℃ of temperature, and that is left bone dry contains auxiliary agent Renyi iron catalyst.The analysis result that contains auxiliary agent Renyi iron catalyst after the drying shows: have 64m
2The granularity of the specific area of/g and 30-200 μ m; With metallic element weight is consisting of of benchmark: 86.4 (weight) % iron, 6.4 (weight) % aluminium, 1.5 (weight) % manganese, 1.8 (weight) % titanium, 0.9 (weight) % potassium.
4. step 3 gained being contained auxiliary agent Renyi iron catalyst is transferred in the fixed bed reactors; activate 8 hours under 0.7NL/gcat/h hydrogen flowing quantity and 350 ℃ of temperature, this catalyst granules that shifts under highly purified nitrogen protection subsequently after activating is to be evaluated to starching in the attitude phase reaction medium.Be applied to the CO+H on this catalyst
2Slurry attitude phase Fischer-Tropsch synthesis condition is: the catalyst grain size of 0.044-0.074mm, and with respect to 15 weight % catalyst concns of reaction medium, 0.7: 1 H
2, CO mol ratio, 260 ℃ reaction temperature and the reaction pressure of 2.5MPa.This contains auxiliary agent Renyi iron catalyst, and the results are shown in Table 1 with the activity rating of representing precipitated iron catalyst under similar reaction condition.
After the catalyst activity evaluation finished, the remaining slurries that contain auxiliary agent Renyi iron catalyst and product wax were used to carry out 60 minutes sedimentation separation test under different temperatures in the reactor, and concrete separating resulting sees table 2 for details.
Embodiment 4
According to preparing catalyst and carry out activity rating with embodiment 3 identical modes.Difference is: with iron, aluminum metal piece, titanium dioxide and manganese sesquioxide managnic oxide by weight 37: 57: 4: 4 mix, and heating and melting in the arc-induced graphite furnace and under the argon shield stirs and makes it even.Thereafter gained iron-aluminium-titanium-manganese liquid alloy is shifted that quenching is to room temperature (15-30 ℃) in the entry, Mechanical Crushing obtains the catalyst alloy granular precursor of 100-3000 μ m granularity.
The auxiliary agent Renyi iron catalyst that contains that finally prepares has 58m
2The granularity of the specific area of/g and 30-200 μ m; With metallic element weight is consisting of of benchmark: 84.6 (weight) % iron, 3.5 (weight) % aluminium, 1.9 (weight) % manganese, 3.2 (weight) % titanium, 0.8 (weight) % potassium.Activity rating and wax separation test result list in respectively in the table 1,2,3.
Embodiment 5
At first with the iron of reguline metal, aluminium and pulverous titanium dioxide, manganese sesquioxide managnic oxide by weight 35: 55: 3: 7 mix, and heating and melting in the arc-induced graphite furnace and under the argon shield forms even molten state alloy.Then the gained liquid alloy is transferred to fast and made it quenching in the cold water to room temperature (15-30 ℃), Mechanical Crushing obtains the catalyst alloy granular precursor of 0.1-3mm granularity.
With alkali lye effect dissolving step 1 gained alloy in the process of metallic aluminium, the same with correlation step among the embodiment 3.
3. be to mix with 50 gram step 2 gained catalyst solid uniform particles subsequently with the methanol solution 50ml that contains the 0.5N potassium ion, under the decompression of 200mmHg and 60 ℃ of temperature conditions, gradually with the evaporation of methyl alcohol and a spot of aqueous solvent, the remaining dry auxiliary agent Renyi iron catalyst that contains.After potassium supports end, under the vacuum protection, will contain auxiliary agent Renyi iron catalyst and mix the formation slurries, to treat next step processing with the atoleine reaction medium.Gained contains auxiliary agent Renyi iron catalyst and has 61m
2The granularity of the specific area of/g and 30-200 μ m; With metallic element weight is consisting of of benchmark: 84.8 (weight) % iron, 3.5 (weight) % aluminium, 1.9 (weight) % manganese, 2.3 (weight) % titanium, 1.5 (weight) % potassium.
4. the slurries that previous step is obtained suddenly are transferred in the Fischer-Tropsch synthesis device stirred tank, and before the evaluation response, this contains auxiliary agent Renyi iron catalyst and need handle less than the 1.0NL/gcat/h hydrogen flowing quantity through 310 ℃ of temperature of 48 hours.And then switch to CO+H
2Synthesis gas carries out Fischer-Tropsch synthesis, and the concrete operations condition is: 0.044-0.074mm contains auxiliary agent Renyi iron catalyst granularity, with respect to 15 weight % catalyst concns of reaction medium, 0.96: 1 H
2, CO mol ratio, 260 ℃ reaction temperature and the reaction pressure of 2.5MPa.This contains the activity rating of auxiliary agent Renyi iron catalyst, and the results are shown in Table 1.
Embodiment 6
At first with the iron of metal bulk, aluminium and pulverous titanium dioxide, manganese sesquioxide managnic oxide by weight 37: 57: 4: 3 mix, are heated to molten state in the arc-induced graphite furnace and under the argon shield, and stirring makes it even.Thereafter gained iron-aluminium-titanium-manganese liquid alloy is quickly transferred in the water, quenching is to room temperature (15-30 ℃), and mechanical crushing is to the catalyst alloy granular precursor of 0.1-3mm granularity.
With alkali lye effect dissolving alloy in metallic aluminium step and to implement in 3 step 2 identical.
3. be evenly to mix with 50 gram catalyst granules subsequently, under 200mmHg negative pressure, 60 ℃ of temperature conditions, methyl alcohol and a spot of aqueous solvent evaporated within 3 hours fully, remain and contain auxiliary agent Renyi iron catalyst for drying with the methanol solution 80ml that contains 0.5N potassium.After potassium supports end, under vacuum, will contain auxiliary agent Renyi iron catalyst and protect the formation slurries with the atoleine reaction medium.The auxiliary agent Renyi iron catalyst that contains that obtains at last has 61m
2The granularity of the specific area of/g and 30-200 μ m; With metallic element weight is consisting of of benchmark: 84.8 (weight) % iron, 2.4 (weight) % aluminium, 2.5 (weight) % manganese, 2.8 (weight) % titanium, 1.5 (weight) % potassium.
It is identical with correlation step among the embodiment 3 to contain the corresponding activation of auxiliary agent Renyi iron catalyst and evaluation procedure.
Embodiment 7
At first with the metal derby of iron, aluminium and titanium dioxide, manganese sesquioxide managnic oxide powder by weight 35: 55: 7.5: 2.5 mix, heating and melting in the arc-induced graphite furnace and under the argon shield, and stir the even liquid alloy of formation.Thereafter liquid alloy is transferred in the water fast, quenching is to room temperature (15-30 ℃), and Mechanical Crushing obtains the catalyst alloy granular precursor of 0.1-3mm granularity.
2. dissolve the step of metallic aluminium in the step 1 gained alloy with alkaline reaction and implement in 3 step 2 identical.
3. be that the methanol solution 50ml of 0.5N potassium and 50 gram step 2 gained catalyst alloy particles are mixed subsequently; under 200mmHg negative pressure and 60 ℃ of temperature conditions; with the evaporation fully within 3 hours of methyl alcohol and low amounts of water solvent, the remaining dry auxiliary agent Renyi iron catalyst that contains.Under vacuum, importing atoleine reaction medium will contain auxiliary agent Renyi iron catalyst and protect afterwards.Final gained contains auxiliary agent Renyi iron catalyst and has 61m
2The granularity of the specific area of/g and 30-200 μ m; With metallic element weight is consisting of of benchmark: 84.8 (weight) % iron, 5.4 (weight) % aluminium, 2.7 (weight) % manganese, 6.1 (weight) % titanium, 1.0 (weight) % potassium.
It is identical with correlation step among the embodiment 3 that gained contains the activation of auxiliary agent Renyi iron catalyst and evaluation procedure.
Embodiment 8
At first with iron, aluminum metal piece, titanium dioxide and manganese sesquioxide managnic oxide powder by weight 35: 55: 2.5: 7.5 mix, heating and melting in the arc-induced graphite furnace and under the argon shield, the careful stirring makes it even.Be transferred to fast then that quenching obtains the Renyi alloy in the water, need obtain the catalyst alloy granular precursor of granularity between 0.1-3mm with the Mechanical Crushing mode.
2. contain the step of auxiliary agent Renyi iron catalyst with alkaline reaction dissolving Aluminum in Alloy with preparation and implement in 3 step 2 identical.
3. be subsequently will contain the methanol solution 200ml and the 50 gram catalyst granules of 0.5N potassium evenly mix, under 200mmHg negative pressure and 60 ℃ of temperature, within 3 hours, methyl alcohol and low amounts of water solvent are evaporated fully, obtain the dry auxiliary agent Renyi iron catalyst that contains.Afterwards need be with the moistening and formation slurries of gained catalyst granules usefulness atoleine reaction medium under vacuum.The auxiliary agent Renyi iron catalyst that contains that obtains like this has 61m
2The granularity of the specific area of/g and 30-200 μ m; With metallic element weight is consisting of of benchmark: 82.5 (weight) % iron, 4.3 (weight) % aluminium, 6.2 (weight) % manganese, 2.1 (weight) % titanium, 4.9 (weight) % potassium.
It is identical with correlation step among the embodiment 3 that gained contains the activation of auxiliary agent Renyi iron catalyst and evaluation procedure.
Table 1
The evaluation test result who contains auxiliary agent Renyi iron catalyst
| Embodiment | *Reference | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Conversion ratio, % CO H 2 | 81.0 74.3 | 74.7 36.2 | 78.2 34.3 | 82.7 58.8 | 76.9 41.1 | 84.8 50.8 | 88.4 59.4 | 81.1 53.3 | 70.5 49.6 |
| Productive rate g/gcat-h C 1-C 2 C 3-C 4， C 5+， C 1+， CO 2Selectivity % C 5+ fraction,＜177 ℃ 177-220 ℃ 220-360 ℃＞360 ℃ | 0.019 0.023 0.264 0.306 47 | 0.032 0.040 0.106 0.178 34 54 13 22 11 | 0.038 0.045 0.178 0.261 42 52 14 28 6 | 0.032 0.041 0.255 0.328 41 43 17 27 13 | 0.043 0.052 0.180 0.275 45 53 15 21 11 | 0.040 0.053 0.199 0.292 47 52 18 19 11 | 0.048 0.053 0.207 0.308 48 54 19 17 10 | 0.042 0.054 0.201 0.297 45 48 19 22 11 | 0.027 0.038 0.185 0.250 44 48 16 23 13 |
*Precipitated iron catalyst, D.B.Bukur, X.Lang, Ind.Eng.Chem.Res., 1999,38,3260-3275
60 minutes plain sedimentation results in the table 2 show that after the raising temperature, the concentration that contains auxiliary agent Renyi iron catalyst in the wax of separating significantly reduces.If after the commercial diesel dilution with 1: 1 volume ratio, even the effect of settling when solid wax product has originally also reached undiluted preceding high temperature when 80 ℃ of temperature.This result of the test shows simultaneously, contain auxiliary agent Renyi iron catalyst and precipitated iron catalyst particle after plain sedimentation is handled, all still have catalyst and heavy wax product to separate, yet at settling efficiency, the catalyst content result who separates under the same terms shows that the auxiliary agent Renyi iron catalyst that contains of the present invention has higher separative efficiency.
Table 2.
The gravitational settling result of the test that contains auxiliary agent Renyi iron catalyst/wax
| Separation test, 1 hour | The sample treatment temperature, ℃ | Separate the catalyst content in the wax of back, wt.% |
| Gu the simple gravitational settling diesel oil of wax dilution back sedimentation in 1: 1 | 150 200 250 80 | 0.182 0.125 0.079 0.085 |
Table 3.
Course of reaction influences the result to containing auxiliary agent Renyi iron catalyst particle size distribution
| Granularity (μ m) | Fresh catalyst | Embodiment 2 (80 hours running backs) | Embodiment 3 (350 hours running backs) | Precipitated iron (450 hours running backs) |
| 44-74 2.5-44 ＜2.5 | 100 0 0 | 86.0 11.8 2.2 | 25.3 71.0 4.7 | 40.0 48.0 *12.0 |
*In the following sample of the reacted catalyst micron of precipitated iron, most particles are in the 10-100 nanometer range.
In table 3, listed after 80 hours and 450 hours and contained auxiliary agent Renyi iron catalyst and use the data of preceding catalyst granules size distribution to compare.
Data from table as can be seen, the fresh auxiliary agent Renyi iron catalyst that contains has the granularity of 44-74 μ m, and after experience 80 hours and running in 450 hours, particle takes place broken, granularity mainly distributes and reduces to the scope of 2.5-44 μ m, and the size distribution of this scope is than being easier in separating.And the result of precipitated iron catalyst after experience running in 450 hours shows, particle is crushed to less than the granularity under the 2.5 μ m apparently higher than containing auxiliary agent Renyi iron catalyst, and this size distribution causes the factor of separation difficulty just.
The present invention has obtained detailed description, and contains with specific that auxiliary agent Renyi iron catalyst is formed and the preparation method is a feature, and the modulation in context of the present invention all is rational.
Claims (10)
- One kind be used for fischer tropsch process contain auxiliary agent Renyi iron catalyst, with this catalyst metals element wt is benchmark, contain the iron of 72.9-90.8 (weight) %, the titanium of 0-6.1 (weight) %, the manganese of 0-8.2 (weight) % and the potassium of 0-4.9 (weight) %, residue is aluminium, and this catalyst has 20-80m 2The granularity of the specific area of/g and 10-10000 μ m.
- 2. the auxiliary agent Renyi iron catalyst that contains as claimed in claim 1, it is characterized in that described catalyst contains the iron of 86.3-90.4 (weight) %, the aluminium of 2.4-9.8 (weight) %, the manganese of 1.5-6.0 (weight) %, the titanium of (1.8-3.2 weight) %, the potassium of 0.8-1.5 (weight) %.
- 3. the auxiliary agent Renyi iron catalyst that contains as claimed in claim 1, the specific area that it is characterized in that described catalyst is 45-65m 2/ g, granularity is 30-200 μ m.
- 4. one kind prepares the method that contains auxiliary agent Renyi iron catalyst that is applied to fischer tropsch process, comprises the steps:1) iron, aluminium and/or titanium, manganese or their oxide with bulk or powdery is mixed together, and this mixture of heating and melting forms the homogeneous phase alloy under atmosphere of inert gases in heater,2) cool off above-mentioned gained alloy fast to 15-20 ℃, with formation catalyst alloy presoma,3) Mechanical Crushing gained catalyst alloy presoma obtains the alloying pellet of the particle size range of 100-10000 μ m, and this alloying pellet contains the iron of 35-55 (weight) %, the aluminium of 40-60 (weight) %, the titanium of 0-10 (weight) % and the manganese of 0-15 (weight) %,4) be the aqueous slkali reaction of 10-50% (weight) with gained catalyst alloy granular precursor and concentration, at alloying pellet with after aqueous slkali contacts fully, temperature kept 50-150 minute at 50-90 ℃, after so the most of aluminium suction filtration in the alloying pellet being fallen, spend deionised water, make that alloying pellet surface liquid pH value is 7, then water is replaced with absolute ethyl alcohol, make and contain auxiliary agent Renyi iron catalyst main body, temporarily be stored in the ethanol stand-by5) will contain auxiliary agent Renyi iron catalyst activates.
- 5. preparation method as claimed in claim 4, it is characterized in that described method also comprises, use a kind of alcoholic solution dipping of potassium above-mentioned obtain contain auxiliary agent Renyi iron catalyst main body, vaporising under vacuum falls all liq solvent subsequently, obtains to support the step that contains auxiliary agent Renyi iron catalyst that potassium is 0.1-4.9 (weight) %.
- 6. preparation method as claimed in claim 4 is characterized in that described catalyst alloy presoma comprises the titanium of manganese and 2 (weight) % of aluminium, 2 (weight) % of iron, 58 (weight) % of 38 (weight) %.
- 7. preparation method as claimed in claim 5 is characterized in that the alcoholic solution of described potassium is selected from the following several solns methanol-hydrogen potassium oxide solution, ethanol-potassium hydroxide solution, ethanol-solution of potassium carbonate.
- 8. preparation method as claimed in claim 5 is characterized in that solvent evaporation that described potassium supports process is to finish under 40-80 ℃ temperature and 100-500mmHg reduced vacuum.
- 9. preparation method as claimed in claim 5 is characterized in that it is by being that the alcoholic solution dipping of the potassium compound of 0.1-0.5N contains auxiliary agent Renyi iron catalyst main body and realizes with a kind of concentration that described potassium supports.
- 10. preparation method as claimed in claim 4 is characterized in that the described activation that contains auxiliary agent Renyi iron catalyst is to carry out hydrogen treat activation or hydrogen or synthesis gas activation on the throne in slurry bed ft synthetic reactor in fixed bed reactors.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101809123A (en) * | 2007-08-10 | 2010-08-18 | Sasol技术股份有限公司 | A hydrocarbon synthesis process |
| CN101796166B (en) * | 2007-08-10 | 2015-01-28 | Sasol技术股份有限公司 | Method of activating a fischer-tropsch catalyst |
| CN114471575A (en) * | 2020-11-13 | 2022-05-13 | 中国科学院大连化学物理研究所 | Catalyst forming method and application thereof |
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2006
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101809123A (en) * | 2007-08-10 | 2010-08-18 | Sasol技术股份有限公司 | A hydrocarbon synthesis process |
| CN101809123B (en) * | 2007-08-10 | 2014-04-30 | Sasol技术股份有限公司 | A hydrocarbon synthesis process |
| CN101796166B (en) * | 2007-08-10 | 2015-01-28 | Sasol技术股份有限公司 | Method of activating a fischer-tropsch catalyst |
| CN114471575A (en) * | 2020-11-13 | 2022-05-13 | 中国科学院大连化学物理研究所 | Catalyst forming method and application thereof |
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