CN1495148A - Adjuvant-containing skeleton iron catalyst for Fischer-Tropsch synthesis process and its preparation method - Google Patents
Adjuvant-containing skeleton iron catalyst for Fischer-Tropsch synthesis process and its preparation method Download PDFInfo
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Abstract
Provided is an adjuvant-containing skeleton iron catalyst, containing 72.0-91.0 wt.% of iron, 0-6.1 wt.% of copper, 0-8.2 wt.% of manganese and 0-4.9 wt.% of kalium and residual aluminium. The process for preparing adjuvant-containing skeleton iron catalyst is: firstly mixing the nubby or powder metal components, heating to molten, forming alloy uniformly, quenching, getting adjuvant-containing alloy procursor except kalium, taking out the great mass of aluminium by lye treatment, loading the kalium on the skeleton iron catalyst by proper alcohol solution of kalium, dipping, drying, processing activating treatment by hydrogen to the adjuvant-containing catalyst. The adjuvant-containing skeleton iron catalyst has a high H2+CO conversion activity, middle distillate selectivity, abrasion resistance and an easy separability from the product wax in the gravity settling condition.
Description
Related application
This application for a patent for invention is the first continuation part of the first two United States Patent (USP), and they are US6277895 of 09/399852 of being numbered that are numbered 09/895621 US6265451 and application in 1999 of calendar year 2001 application.
Invention field
Invention is used for by CO, H
2It is main synthetic gas is converted into the plurality of target hydrocarbon product through the Fischer-Tropsch building-up process the skeletal iron catalyst that contains auxiliary agent.Particularly, the present invention relates to have specific composition and contain the auxiliary agent skeletal iron catalyst, improvement is all arranged aspect the advantage of the catalyzer suitable slurry attitude bed catalyticreactors such as bottoms product productive rate, catalyzer abrasion resistance and catalyst sedimentation efficient in raising after wherein optimizing through what multipath optimization made.The invention still further relates to this Preparation of catalysts method.
Background of invention
Fischer-Tropsch catalysis building-up process is well-knownly will contain CO, H
2It is the effective way that main synthetic gas is converted into chemical feedstocks and liquid hydrocarbon product.Wherein the application of precipitated iron catalyst in this technology obtained broad research, and can reach higher catalytic activity, but but is very easy to be broken into micron particles in the reactor operation of producing the liquid hydrocarbon product.Grain breakage has caused the difficult problem when separating thin granules of catalyst and liquid hydrocarbon product and wax like this, has therefore hindered the process of industrialization of Fischer-Tropsch building-up process.Recently, some are open at skeletal iron catalyst United States Patent (USP)s of this process, i.e. the US6265451 of Zhou etc., US6277895.But still need further improve this skeletal iron catalyst.
The auxiliary agent skeletal iron catalyst that contains of the present invention has the good performance that is applied to industrialization Fischer-Tropsch building-up process, mainly refer to be used for paste state bed reactor, this is because catalyzer of the present invention has in the low cost, paste state bed reactor of units activity metal granules of catalyst polishing machine good under the fierce fluid state etc.And, this catalyzer easily and Fischer-Tropsch synthetic wax product separate through method such as gravity settling or filtration.
Brief summary of the invention
This invention provides contains copper, manganese and the potassium etc. that the auxiliary agent skeletal iron catalyst mainly comprises iron and amount of auxiliary.With the weight that contains the auxiliary agent skeletal iron catalyst is benchmark, and this contains the auxiliary agent skeletal iron catalyst and contains 72.0-91.0 (weight) % iron, 0-6.1 (weight) % copper, 0-8.2 (weight) % manganese and 0-4.9 (weight) % potassium, and all the other then are aluminium.This surface-area that contains the auxiliary agent skeletal iron catalyst is at 20-80m
2/ g scope, 45-65m more fortunately
2/ g, size-grade distribution is at 10-10000 μ m, 30-200 μ m more fortunately.This contains the auxiliary agent skeletal iron catalyst and has good granule strength 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 activity that contains the auxiliary agent skeletal iron catalyst is suitable with typical precipitated iron catalyst, and all good on the diesel product selectivity than precipitated iron and molten iron, this contains, and the auxiliary agent skeletal iron catalyst can be applied to fixed bed or paste state bed reactor synthesizes to come production purpose hydrocarbon product with Fischer-Tropsch.Its gained hydrocarbon liquids product has rich alpha-olefin characteristics, can be used as the high industrial chemicals of economic worth.
The present invention contains the auxiliary agent skeletal iron catalyst and makes by improved method, that is, with the metal or the compound of bulk or powdered iron, aluminium and/or copper and manganese, heated mixt cools off this molten alloy fast to room temperature state to molten state, be generally 15-20 ℃, for example water quenching etc.; Then prepared alloy is broken for the granularity of 100-10000 μ m.Thereafter, the most of aluminium in the alloy is removed with suitable alkaline solution such as NaOH or KOH suction filtration, forms ferrum-based catalyst.This ferrum-based catalyst is subsequently by flooding the solution of potassium, to support the potassium of 0-4.9 (weight) %.This contain the auxiliary agent skeletal iron catalyst can be in fixed-bed reactor or in the paste state bed reactor one's own department or unit high-temperature activation, the gained catalyzer possesses by H
2Transform to generate the greater activity of multiple desirable hydrocarbon product reaction with the CO unstripped gas and in operation good abrasion resistance, and the unlikely following grain graininess of micron order that is broken into.And because the higher characteristics of density of catalyst system therefor separate with hydrocarbon product through gravity settling easily, therefore, the Fischer-Tropsch synthesis process of the suitable especially paste state bed reactor of this catalyzer.
The auxiliary agent skeletal 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 improvement to original skeletal iron catalyst.These advantages show preparation method's simplification, promptly, the alloy of metal block preparation that uses volume particle size through fusion, be cooled to room temperature, be crushed to required particle size and obtain catalyst precursor, also show simultaneously and adopt improved method that potassium promoter is supported on the catalyzer.This catalyzer can pass through in fixed bed or the effective activation on the throne of slurry attitude bed.Gained contains the auxiliary agent skeletal iron catalyst particularly can reach high synthetic gas transformation efficiency (CO transformation efficiency＞80%) in the paste state bed reactor under the industrial reaction condition, suitable with representational precipitated iron, and have suitable stabilizing active and better fluid fuel and alpha-olefin selectivity.And catalyzer of the present invention possesses good abrasion resistance, generates the liquid hydrocarbon product through settlement separate performance with the syrup state bed Fischer Tropsch reactor.
Summary of the invention
The present invention relates to a kind ofly have specific composition and be applied to through the Fischer-Tropsch building-up reactions by H
2Contain the auxiliary agent skeletal iron catalyst with the CO unstripped gas generates purpose liquid hydrocarbon product process.With the weight that contains the auxiliary agent skeletal iron catalyst is benchmark, and the auxiliary agent skeletal iron catalyst that contains of the present invention contains 72.0-91.0 (weight) % iron, 0-6.1 (weight) % copper, 0-8.2 (weight) % manganese and 0-4.9 (weight) % potassium, and all the other then are aluminium.This surface-area that contains the auxiliary agent skeletal iron catalyst is at 20-80m
2/ g scope, 45-65m more fortunately
2/ g, size-grade distribution is at 10-10000 μ m, 30-200 μ m more fortunately.
Contain the auxiliary agent skeletal iron catalyst preferably and comprise 86.3-90.4 (weight) % iron, 2.4-9.8 (weight) % aluminium, 1.5-6 (weight) % manganese, 0.8-1.5 (weight) % potassium, specific surface area is 45-65m
2/ g, granularity is 30-200 μ m.
The best auxiliary agent skeletal iron catalyst that contains comprises 90.8 (weight) % iron, 2.4 (weight) % aluminium, 2.5 (weight) % manganese, 2.8 (weight) % copper, 1.5 (weight) % potassium.
The method for preparing this catalyzer comprises following 5 steps:
1) bulk or powdered iron, aluminium and/or copper, manganese or their compound are mixed together, this mixture of heating and melting forms alloy under inert atmosphere in appropriate device;
2) cool off above-mentioned gained alloy fast to room temperature, be generally 15-20 ℃, to form catalyst precursor;
3) Mechanical Crushing gained alloy presoma is to the size range of 100-10000 μ m;
4) be the appropriate base solution of 10-50% with gained catalyst precursor particles and suitable concentration, for example sodium hydroxide or potassium hydroxide reaction, at alloying pellet with after alkali lye contacts fully, temperature kept 50-150 minute at 50-90 ℃, after so the most of aluminium suction filtration in the alloying pellet being removed, with alloying pellet to the pH value after the deionized water wash processing is 7, then with dehydrated alcohol water is replaced, and is stored in the dehydrated alcohol stand-by.
5) this contains the auxiliary agent skeletal iron catalyst and carries out activation treatment, and activation condition is 0.05-1.0NL/gcat/h hydrogen flowing quantity, 310-350 ℃ service temperature, treatment time 2-12 hour.
Can also support potassium in above-mentioned containing on the auxiliary agent skeletal iron catalyst main body of obtaining.Use the above-mentioned skeletal iron catalyst main body that obtains of a kind of suitable potassium promoter alcoholic solution dipping, subsequently vaporising under vacuum fall all liquid solvent with obtain to support potassium be 0.1-4.9 (weight) % contain the auxiliary agent skeletal iron catalyst.
In the preparation process that contains the auxiliary agent skeletal iron catalyst: at first with the piece or the powder of iron block or powder and required non-ferrous metal such as aluminium, copper, manganese, in 20-80 (weight) % iron and the non-ferrous components ratio of 30-70 (weight) % uniform mixing, typical blending ratio scope is (weight): 35-55% iron, 40-60% aluminium, 1-15% manganese, 0-10% copper.This mixture to forming a molten state alloy, then adopts the method for water quenching to be quickly cooled to room temperature through heating and melting, is generally 15-20 ℃.Obtain the catalyst precursor of granularity through fragmentation at 10-10000 μ m.Catalyst precursor consists of: 35-55 (weight) % iron, 40-60 (weight) % aluminium, 0-10 (weight) % copper and 1-15 (weight) % manganese.This 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 reactivity, most aluminium suction filtration is gone out, be left promptly to contain substantially auxiliary agent skeleton iron skeleton iron catalyst.
Gained contains the auxiliary agent skeletal iron catalyst can also be transferred in the suitable potassic alcoholic solution and flood, and then alcoholic solvent is evaporated, form support 0.1-1.5 (weight) % potassium contain the auxiliary agent skeletal iron catalyst.The alcoholic solution of suitable potassium includes but not limited to: methanol-hydrogen potassium oxide, ethanol-potassium hydroxide, salt of wormwood-water-alcohol etc.
Gained contains the auxiliary agent skeletal 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, 310-350 ℃, 2-12 hour, and then for example whiteruss or ethanol are transferred in the reactor stand-by via suitable reaction medium.Equally, this skeletal iron catalyst that contains auxiliary agent also can be at first with reaction medium for example whiteruss 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, 310-350 ℃ temperature, 3-48 hour, finish reactivation process with hydrogen.Like this, H can be used and use to this skeletal iron catalyst effectively
2With the process of CO unstripped gas through Fischer-Tropsch building-up reactions generation purpose hydrocarbon product.
The particle that contains the auxiliary agent skeletal iron catalyst that finally obtains is in the 10-10000 mu m range, and wherein the particle in the 1000-10000 scope can be used for fixing bed bioreactor, then can be used for paste state bed reactor at the small-particle of 20-200 mu m range.
Therefore.The present invention contains auxiliary agent skeletal iron catalyst whole process of preparation and is divided into following a few part:
1. contain the preparation of auxiliary agent skeletal iron catalyst presoma
The fast shape of piece or powdered iron and non-ferrous metal component are pressed 35-55 (weight) % iron, 40-60 (weight) % aluminium and copper, 5-15 (weight) % manganic compound powder forms mixture.In a device that suits, as electric arc induction furnace, the heating of metal mixture is treated to be quickly cooled to room temperature after alloy molten liquid evenly to the molten state alloy, adopt the method for water or other liquid quench to cool off fast then, be less than 10 seconds time internal cooling to 15-20 ℃.Be the scope of granularity with the Mechanical Crushing method with the screening of gained alloy at last at 10-10000 μ m.
2. contain the preparation of auxiliary agent skeletal iron catalyst main body
The process that is prepared skeletal iron catalyst by this iron alloy 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 alloying pellet (10-10000 μ m granularity) in the solution then, treat that alloying pellet adds the back that finishes and keeps being reflected at the little 2-150 of controlled condition minute, so that the most of aluminium in the alloy is gone out by suction filtration.The alloying pellet that then uses deionized water wash to handle reaches or near 7, then with dehydrated alcohol water is replaced until the pH value, and resulting main body is contained the auxiliary agent skeletal iron catalyst is stored in the dehydrated alcohol.
3. contain the activation of auxiliary agent skeletal iron catalyst
Through containing the auxiliary agent skeletal 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 skeletal iron catalyst transfer of granules to fixed-bed reactor; after the hydrogen treat activation; again be transferred in the fischer-tropsch reactor; wherein transfer process needs the protection of rare gas element; activation condition in fixed bed is: 0.05-1.0NL/gcat/h hydrogen; 310-350 ℃ of temperature, 2-12 hour treatment time.
Perhaps, the dried auxiliary agent skeletal iron catalyst particle that contains can be by with a certain amount of reaction medium whiteruss formation slurries for example, be transferred to activation on the throne in the fischer-tropsch reactor then, used condition is: the 0.3-3.0NL/gcat/h hydrogen flowing quantity, 310-350 ℃ of temperature handled 3-48 hour.
Main body contains supporting of potassium on the auxiliary agent skeletal iron catalyst
The main body that obtains contains the auxiliary agent skeletal iron catalyst and can also by following operation potassium be flooded up before activation: the alcoholic solution that at first will prepare a potassium, the for example carbonic acid of potassium or salpeter solution, potassium content wherein is to decide with respect to the part by weight of iron level in the catalyzer, i.e. 0.5-4.9 potassium: 100 iron.The alcoholic solution of skeletal iron catalyst main body and the preparation of this method to be mixed then and put into rotatory evaporator, below under the condition, 40-80 ℃ of temperature, the 100-500mmHg negative pressure is done the alcoholic solution evaporation, and what obtain that exsiccant is impregnated with potassium contains the auxiliary agent skeletal iron catalyst.
Contain the application of auxiliary agent skeletal iron catalyst in Fischer-Tropsch synthesis
The described auxiliary agent skeletal iron catalyst that contains of this invention is to containing CO and H
2Unstripped gas is extremely effective through the process that the Fischer-Tropsch building-up reactions generates required hydrocarbon product, especially for slurry attitude phase reactor.Effectively operation condition is: H
2/ CO mol ratio is 0.5-5: 1, catalyst weight concentration 5-40% (with respect to reaction medium whiteruss for example), fixed-bed reactor are used the 1-10mm grain graininess, slurry attitude phase reactor is adopted the granularity of 20-200 μ m, reaction pressure is at 1.0-3.0MPa, and the gas space velocity flow is 0.5-5.0NL/gcat/h.Can granules of catalyst fundamental sum product liquid be separated by the gravity settling operation behind purpose product liquid hydrocarbon and the catalyst system therefor particulate emission.
Adopt the prepared application performance that contains the auxiliary agent skeletal iron catalyst of improving one's methods to illustrate by following examples of implementation in this invention, but be not limited to these examples.
Embodiment 1
1. at first iron, aluminum metal piece are pressed the metal weight ratio and mixed at 40: 60, in electric arc induction furnace He under the argon shield, be heated to molten state, stir and make it even.Thereafter gained iron-aluminium liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 100-3000 μ m granularity with the Mechanical Crushing mode.
2. under hydrogen atmosphere, the NaOH solution of placing a certain amount of 25% concentration in advance is heated to 55 ℃ in a special container, slowly to wherein adding alloying pellet.The interpolation alloy finishes, and back maintenance reaction conditions is constant to continue 90 minutes, so that the most of aluminium suction filtration in the alloy is gone out.Then the alloying pellet of handling with deionized water wash to the pH value near or reach 7, and temporarily be stored in the ethanol after replacing water with dehydrated alcohol.The skeletal iron catalyst that obtains after this step has 45m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 72.9 (weight) % iron, 27.1 (weight) % aluminium.
3. the gained skeletal iron catalyst is transferred in the fixed-bed reactor, activation is 8 hours under 0.7NL/gcat/h hydrogen flowing quantity and 350 ℃ of temperature, subsequently under highly purified nitrogen protection with the catalyst activated transfer of granules in slurry attitude phase reaction medium.Be applied to the CO+H on this catalyzer
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, 270 ℃ temperature of reaction and the reaction pressure of 2.5MPa.The results are shown in Table 1 with the activity rating of correlated precipitated iron catalyst under similar reaction conditions for this skeletal iron catalyst.
Embodiment 2
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 38: 58: 2: 2 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 100-3000 μ m granularity with the Mechanical Crushing mode.
2. under hydrogen atmosphere, the NaOH solution of placing a certain amount of 25% concentration in advance is heated to 75 ℃ in a special container, slowly to wherein adding alloying pellet.The interpolation alloy finishes, and back maintenance reaction conditions is constant to continue 90 minutes, so that the most of aluminium suction filtration in the alloy is gone out.Then the alloying pellet of handling with deionized water wash to the pH value near or reach 7, and temporarily be stored in the ethanol after replacing water with dehydrated alcohol.Gained contains the auxiliary agent skeletal iron catalyst and has 54m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 86.9 (weight) % iron, 9.8 (weight) % aluminium, 1.5 (weight) % manganese, 1.8 (weight) % copper.
3. gained being contained the auxiliary agent skeletal iron catalyst is transferred in the fixed-bed reactor; 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 catalyzer
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, 270 ℃ temperature of reaction and the reaction pressure of 2.5MPa.This contains the auxiliary agent skeletal iron catalyst, and the results are shown in Table 1 with the activity rating of correlated precipitated iron catalyst under similar reaction conditions.
After the catalyst activity evaluation finished, the remaining slurries that contain auxiliary agent skeletal iron catalyst and product wax were used to carry out 15 minutes gravity settling separation test under differing temps in the reactor, and concrete separating resulting sees table 2 for details.
Embodiment 3
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 38: 58: 2: 2 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 100-3000 μ m granularity with the Mechanical Crushing mode.
2. under hydrogen atmosphere, the NaOH solution of placing a certain amount of 25% concentration in advance is heated to 75 ℃ in a special container, slowly to wherein adding alloying pellet.The interpolation alloy finishes, and back maintenance reaction conditions is constant to continue 90 minutes, so that the most of aluminium suction filtration in the alloy is gone out.Then the alloying pellet of handling with deionized water wash to the pH value near or reach 7, and temporarily be stored in the ethanol after replacing water with dehydrated alcohol.
3. be the methanol solution of preparation potassium (selecting salt of wormwood for use) subsequently, and mix that specifically proportioning is that the weight ratio according to potassium and iron is 2: 100 with the auxiliary agent skeletal iron catalyst particle that contains after handling.Gradually pure and mild a spot of water solvent is evaporated under 200mmHg vacuum tightness, 60 ℃ of temperature, remaining exsiccant contains the auxiliary agent skeletal iron catalyst.The analytical results that contains the auxiliary agent skeletal iron catalyst after the drying shows: have 64m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 90.4 (weight) % iron, 5.4 (weight) % aluminium, 1.5 (weight) % manganese, 1.8 (weight) % copper, 0.9 (weight) % potassium.
4. gained being contained the auxiliary agent skeletal iron catalyst is transferred in the fixed-bed reactor; activate 8 hours under 0.7NL/gcat/h hydrogen flowing quantity and 350 ℃ of temperature, it is to be evaluated to starching in the attitude phase reaction medium to shift the catalyst activated particle subsequently under highly purified nitrogen protection.Be applied to the CO+H on this catalyzer
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, 270 ℃ temperature of reaction and the reaction pressure of 2.5MPa.This contains the auxiliary agent skeletal iron catalyst, and the results are shown in Table 1 with the activity rating of representing precipitated iron catalyst under similar reaction conditions.
After the catalyst activity evaluation finished, the remaining slurries that contain auxiliary agent skeletal iron catalyst and product wax were used to carry out 15 minutes gravity settling separation test under differing temps in the reactor, and concrete separating resulting sees table 2 for details.
The relevant settlement separate test of this catalyzer further compares with a typical precipitated iron sample, is 15 minutes result of sedimentation under differing temps equally, sees table 3 for details.
Embodiment 4
According to preparing catalyzer and carry out activity rating with embodiment 3 identical modes.Difference is: iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 37: 57: 4: 4 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 100-3000 μ m granularity with the Mechanical Crushing mode.
The auxiliary agent skeletal iron catalyst that contains that obtains has 58m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 90.6 (weight) % iron, 3.5 (weight) % aluminium, 1.9 (weight) % manganese, 3.2 (weight) % copper, 0.8 (weight) % potassium.Activity rating and wax separation test result list in respectively in the table 1,2,3.
Embodiment 5
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 35: 55: 3: 7 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 0.1-3mm granularity with the Mechanical Crushing mode.
2. be the process of suction filtration Aluminum in Alloy, the same with correlation step among the embodiment 3.
3. the process that supports of potassium is also the same with correlation step among the embodiment 3 subsequently, and gained contains the auxiliary agent skeletal iron catalyst and has 61m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 90.8 (weight) % iron, 3.5 (weight) % aluminium, 1.9 (weight) % manganese, 2.3 (weight) % copper, 1.5 (weight) % potassium.
4. the slurries that previous step is obtained suddenly are transferred in the Fischer-Tropsch synthesis device stirring tank, and before the evaluation response, this contains the auxiliary agent skeletal iron catalyst and need handle through 310 ℃ of temperature 1.0NL/gcat/h hydrogen streams of 48 hours.And then switch to CO+H
2Synthetic gas carries out Fischer-Tropsch synthesis, and the concrete operations condition is: 0.044-0.074mm contains auxiliary agent skeletal iron catalyst granularity, with respect to 15 weight % catalyst concns of reaction medium, 0.96: 1 H
2, CO mol ratio, 270 ℃ temperature of reaction and the reaction pressure of 2.5MPa.This contains the activity rating of auxiliary agent skeletal iron catalyst, and the results are shown in Table 1.
Embodiment 6
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 37: 57: 4: 3 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 0.1-3mm granularity with the Mechanical Crushing mode.
2. to contain in the step of auxiliary agent skeletal iron catalyst skeleton main body and the enforcement 3 step 2 identical for suction filtration Aluminum in Alloy preparation.
Potassium subsequently support step also with embodiment 3 in relevant step the same, the auxiliary agent skeletal iron catalyst that contains that obtains at last has 61m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 90.8 (weight) % iron, 2.4 (weight) % aluminium, 2.5 (weight) % manganese, 2.8 (weight) % copper, 1.5 (weight) % potassium.
It is identical with correlation step among the embodiment 3 to contain the activation of auxiliary agent skeletal iron catalyst and evaluation.
Embodiment 7
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 35: 55: 7.5: 2.5 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 0.1-3mm granularity with the Mechanical Crushing mode.
2. to contain in the step of auxiliary agent skeletal iron catalyst skeleton main body and the enforcement 3 step 2 identical for suction filtration Aluminum in Alloy preparation.
3. be with the alcoholic solution 50ml and the 50 gram granules of catalyst uniform mixing of the potassium compound of 0.5N subsequently, under 200mmHg vacuum tightness, 60 ℃ of temperature, gradually pure and mild a spot of water solvent evaporated that remaining exsiccant contains the auxiliary agent skeletal iron catalyst.After supporting end, under the vacuum tightness protection, will contain the auxiliary agent skeletal iron catalyst and mix the formation slurries, to treat next step processing with the whiteruss reaction medium.The auxiliary agent skeletal iron catalyst that contains that obtains at last has 61m
2The granularity of the specific surface area of g/ and 30-200 μ m; Consist of: 84.8 (weight) % iron, 5.4 (weight) % aluminium, 2.7 (weight) % manganese, 6.1 (weight) % copper, 1.0 (weight) % potassium.
It is identical with correlation step among the embodiment 3 to contain the activation of auxiliary agent skeletal iron catalyst and evaluation.
Embodiment 8
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 35: 55: 2.5: 7.5 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 0.1-3mm granularity with the Mechanical Crushing mode.
2. to contain in the step of auxiliary agent skeletal iron catalyst skeleton main body and the enforcement 3 step 2 identical for suction filtration Aluminum in Alloy preparation.
3. be with the alcoholic solution 200ml and the 50 gram granules of catalyst uniform mixing of the potassium compound of 0.5N subsequently, under 200mmHg vacuum tightness, 60 ℃ of temperature, gradually pure and mild a spot of water solvent evaporated that remaining exsiccant contains the auxiliary agent skeletal iron catalyst.After supporting end, under the vacuum tightness protection, will contain the auxiliary agent skeletal iron catalyst and mix the formation slurries, to treat next step processing with the whiteruss reaction medium.The auxiliary agent skeletal iron catalyst that contains that obtains at last has 61m
2The granularity of the specific surface area of/g and 30-200 μ m; Consist of: 82.5 (weight) % iron, 4.3 (weight) % aluminium, 6.2 (weight) % manganese, 2.1 (weight) % copper, 4.9 (weight) % potassium.
It is identical with correlation step among the embodiment 3 to contain the activation of auxiliary agent skeletal iron catalyst and evaluation.
Embodiment 9
1. at first iron, aluminum metal piece, cupric oxide and manganous carbonate were pressed the metal weight ratio 34: 54: 2: 10 mix, and are heated to molten state in electric arc induction furnace He under the argon shield, stir and make it even.Thereafter gained iron-Solder for Al-Cu Joint Welding-manganese liquid alloy is poured fast in the water into quenching to room temperature (15-20 ℃), then obtained the catalyst precursor particles of 0.1-3mm granularity with the Mechanical Crushing mode.
2. to contain in the step of auxiliary agent skeletal iron catalyst skeleton main body and the enforcement 3 step 2 identical for suction filtration Aluminum in Alloy preparation.
3. be with the alcoholic solution 50ml and the 50 gram granules of catalyst uniform mixing of the potassium compound of 0.5N subsequently, under 200mmHg vacuum tightness, 60 ℃ of temperature, gradually pure and mild a spot of water solvent evaporated that remaining exsiccant contains the auxiliary agent skeletal iron catalyst.After supporting end, under the vacuum tightness protection, will contain the auxiliary agent skeletal iron catalyst and mix the formation slurries, to treat next step processing with the whiteruss reaction medium.The auxiliary agent skeletal iron catalyst that contains that obtains at last has 61m
2The granularity of the specific surface area of g/ and 30-200 μ m; Consist of: 83.2 (weight) % iron, 5.6 (weight) % aluminium, 8.2 (weight) % manganese, 1.9 (weight) % copper, 1.1 (weight) % potassium.It is identical with correlation step among the embodiment 3 to contain the activation of auxiliary agent skeletal iron catalyst and evaluation.
Table 1
The evaluation test result who contains the auxiliary agent skeletal iron catalyst
| Embodiment | *Precipitated iron 123456789 |
| The reaction conditions temperature, ℃ air speed, NL/gcat-h H 2/CO，mol. | ?260??????270????270????270????270????270????270????270???270???270 ?1.8??????1.5????3.0????3.0????2.0????2.0????2.0????2.0???2.0???2.0 ?0.68?????2.0????2.0????0.70???1.23???1.04???1.00???1.00??1.00??1.00 |
| Transformation efficiency .% CO H 2??H 2/ CO utilizes ratio, | ?81.0?????74.7???77.7???82.5???68.9???76.8???88.4???84.1??70.5??73.0 ?74.3?????36.2???33.1???62.8???38.1???50.8???59.4???58.3??49.6??47.1 ?0.74?????0.97???0.85???0.53???0.75???0.69???0.66???0.69??0.70??0.64 |
| Products distribution C 1-C 2g/gCat-h ??C 3-C 4g/gCat-h ??C 5+C 6g/gCat/h ??C 7+C 8g/gCat-h ??CO 2(Conv′d?CO) ??C 5+ fraction, wt%＜177 ℃ 177-220 ℃ 220-360 ℃＞360 ℃ | ?0.019????0.03???0.05???0.05???0.04???0.02???0.04???0.05??0.03??0.04 ?0.023????0.04???0.07???0.07???0.05???0.03???0.05???0.06??0.03??0.06 ?0.264????0.10???0.20???0.21???0.19???0.15???0.20???0.21??0.22??0.19 ?0.306????0.17???0.33???0.34???0.28???0.21???0.30???0.32??0.28??0.29 ?0.47?????0.34???0.31???0.47???0.40???0.51???0.46???0.44??0.47??0.46 ??????????54?????52?????44?????53?????56?????51?????53????48????55 ??????????13?????14?????17?????13?????10?????14?????14????15????14 ??????????22?????28?????27?????21?????17?????21?????19????23????20 ??????????11?????6??????12?????13?????17?????14?????14????14????11 |
*D.B.Bukur，X.Lang，Ind.Eng.Chem.Res.，1999，38，3270-3275
Table 2. contains the gravity settling test-results of auxiliary agent skeletal iron catalyst/wax
| Separation test sample treatment temp is separated the catalyst content in the wax of back, ℃ wt.% |
| The dilution back sedimentation 30 0.096 in 1: 1 of simple gravity settling 130 0.132 (3 different tests) 185 0.085 205 0.069 hexanes |
15 minutes sedimentation results in the table 2 show, along with the raising of system temperature, also sedimentation is obvious to be present in the auxiliary agent skeletal iron catalyst particle that contains in the wax.And, when the wax sample after the hexane dilution of using 1: 1 volume ratio can reach during 30 ℃ of temperature undiluted before effect of settling during high temperature.
Table 3
Contain the settlement separate test of auxiliary agent skeletal iron catalyst and precipitated iron catalyst relatively
| Solid concentration in the slurries, wt% | HTI-skeleton iron 15 | Precipitated iron (U.S. one research institution) 3.0 |
| The sample treatment temp, ℃ | Separate the solids content in the wax of back, and wt% (solid settlement efficient, wt%) | |
| ??130 ??185 ??205 | ????0.132(99.12) | ????1.372(54.33) |
| ????0.085(99.43) | ????0.938(68.66) | |
| ????0.069(99.54) | ????0.882(70.66) | |
Separation test result from table 3 can find, contain auxiliary agent skeletal iron catalyst and precipitated iron catalyst particle all along with the increase of temperature has significant sedimentation although be present in the wax, but, with regard to settling efficiency, be the per-cent of the content of the settlement separate catalyst content of opening before with respect to sedimentation, it is obviously very high to contain the auxiliary agent skeletal iron catalyst.
Table 4
Reaction process influences the result to containing auxiliary agent skeletal iron catalyst particle size distribution
| Granularity live catalyst embodiment 2 embodiment 3 precipitated iron (μ m) (100 hours running backs) (500 hours running backs) (500 hours running backs) |
| 44-74????100???????89.0????????????24.7????????????40.0 2.5-44???0?????????9.8?????????????70.0????????????48.0 ＜2.5????0?????????1.2?????????????5.3?????????????12.0 |
In table 4, also listed after 100 hours and 500 hours and contained the auxiliary agent skeletal iron catalyst and use the data of preceding granules of catalyst size-grade distribution to compare.
Data from table as can be seen, freshly contain the granularity that the auxiliary agent skeletal iron catalyst has 44-74 μ m, after experience 100 hours and running in 500 hours, fragmentation takes place in particle, granularity mainly distributes and reduces to the scope of 2.5-44 μ m, and the size-grade distribution of this scope is than being easier in isolating.And precipitated iron catalyst the experience 500 hours the running after the result show, grain breakage to less than the granularity under the 2.5 μ m apparently higher than containing the auxiliary agent skeletal iron catalyst, this size-grade distribution causes the factor of separation difficulty just.
Although this invention has obtained detailed description, and contain with specific that the auxiliary agent skeletal iron catalyst is formed and the preparation method is a feature, the modulation in this summary of the invention scope all is rational, specifically according to following claims content.
Claims (21)
- One kind be used for Fischer-Tropsch synthesis contain the auxiliary agent skeletal iron catalyst, with this catalyst weight is benchmark, contain the iron of 72.0-91.0 (weight) %, the copper of 0-6.1 (weight) %, the manganese of 0-8.2 (weight) % and the potassium of 0-4.9 (weight) %, remain and be aluminium; This catalyzer has 20-80m 2The granularity of the specific surface area of/g and 10-10000 μ m.
- 2. the auxiliary agent skeletal iron catalyst that contains as claimed in claim 1, the iron that it is characterized in that containing of described catalyzer: 86.3-90.8 (weight) %, the aluminium of 2.4-9.8 (weight) %, the manganese of 1.5-6.0 (weight) %, the copper of (1.8-3.2 weight) %, the potassium of 0.8-1.5 (weight) %.
- 3. the auxiliary agent skeletal iron catalyst that contains as claimed in claim 1, the specific surface area that it is characterized in that described catalyzer is 45-65m 2/ g, granularity is 30-200 μ m.
- 4. one kind prepares the method that contains the auxiliary agent skeletal iron catalyst that is applied to Fischer-Tropsch synthesis process, comprises following 5 steps:1) bulk or powdered iron, aluminium, copper or its compound, manganic compound are mixed together, this mixture of heating and melting forms alloy under atmosphere of inert gases;2) cool off above-mentioned gained alloy fast to 15-20 ℃, to form catalyst precursor;3) Mechanical Crushing gained alloy presoma obtains the size range of 100-10000 μ m;4) be the alkaline solution reaction of 10-50% (weight) with gained catalyst precursor particles and concentration, at alloying pellet with after alkali lye contacts fully, temperature kept 50-150 minute at 50-90 ℃, after so the most of aluminium suction filtration in the alloying pellet being fallen, is 7 with the alloying pellet after the deionized water wash processing to the pH value, then water is replaced, temporarily be stored in the ethanol stand-by with dehydrated alcohol;5) this contains the auxiliary agent skeletal iron catalyst and carries out activation treatment, and activation condition is 0.05-1.0NL/gcat/h hydrogen flowing quantity, 310-350 ℃ service temperature, treatment time 2-12 hour.
- 5. 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 skeletal iron catalyst main body, vaporising under vacuum falls all liquid solvent subsequently, obtains to support the step that contains the auxiliary agent skeletal iron catalyst that potassium is 0-4.9 (weight) %.
- 6. preparation method as claimed in claim 4 is characterized in that described catalyzer consists of: 90.8 weight % iron, 2.4 weight % aluminium, 2.5 weight % manganese, 2.8 weight % copper, 1.5 weight % potassium.
- 7. preparation method as claimed in claim 4, the type of cooling that it is characterized in that described alloy molten attitude adopt the method for water quenching, are being less than 10 seconds time internal cooling to 15-20 ℃.
- 8. preparation method as claimed in claim 4 is characterized in that the described auxiliary agent skeletal iron catalyst main body that contains, and before supporting potassium, is exposed among the air for preventing granules of catalyst, need be sized to the size range of requirement in alcoholic solvent.
- 9. 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.
- 10. 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 vacuum, the loading of final potassium is 0-4.9 (weight) %.
- 11. preparation method as claimed in claim 5 is characterized in that it is by being that the alcoholic solution impregnated skeleton iron catalyst of the potassium compound of 0.1-0.5N is realized with a kind of concentration that described potassium promoter supports.
- 12. preparation method as claimed in claim 4, it is characterized in that described method also comprises contains the activatory step of auxiliary agent skeletal iron catalyst in fixed-bed reactor with this, and activation condition is 0.05-1.0NL/gcat/h hydrogen flowing quantity, 310-350 ℃ service temperature, treatment time 2-12 hour; With reaction medium this catalyzer is transferred in the slurry attitude phase Fischer-Tropsch synthesis device again.
- 13. preparation method as claimed in claim 4, it is characterized in that described method also comprises contains auxiliary agent skeletal iron catalyst activatory step on the throne in slurry bed ft synthetic reactor with this, this step is for to be transferred to dried catalyzer in the reactor with reaction medium under rare gas element, and processing was finished in 3-48 hour under 310-350 ℃ of temperature, 0.3-3.0NL/gcat/h hydrogen flowing quantity.
- 14. preparation method as claimed in claim 13 is characterized in that the described auxiliary agent skeletal iron catalyst that contains is by adopting whiteruss to be transferred in the reactor activatory on the throne subsequently.
- 15. a use contains the Fischer-Tropsch synthesis method that the auxiliary agent skeletal iron catalyst is produced liquid hydrocarbon product according to claim 1, this method comprises the following steps:1) employing contains H 2With CO and with H 2/ CO mol ratio is 0.5-5: 1 unstripped gas enters reaction medium and the described reactor that contains the auxiliary agent skeletal iron catalyst of claim 1 is housed, and the operational condition of reactor is: the gas flow rate of 200-350 ℃ of temperature, 1.0-3.0MPa pressure, 0.5-5.0NL/gcat/h;2) by discharging gaseous state and the liquefied hydrocarbon product that comprises granules of catalyst in the above-mentioned reactor.
- 16. Fischer-Tropsch synthesis method as claimed in claim 16 is characterized in that described reactant is paste state bed reactor or fixed-bed reactor.
- 17. Fischer-Tropsch synthesis method as claimed in claim 15 is characterized in that in the described Fischer-Tropsch synthesis process, is 1000-10000 μ m in the used granularity that contains the auxiliary agent skeletal iron catalyst of fixed-bed reactor.
- 18. Fischer-Tropsch synthesis method as claimed in claim 15 is characterized in that in the described Fischer-Tropsch synthesis process, is 20-200 μ m in the used granularity that contains the auxiliary agent skeletal iron catalyst of paste state bed reactor.
- 19. Fischer-Tropsch synthesis method as claimed in claim 15 is characterized in that the used weight concentration with respect to used reaction medium that contains the auxiliary agent skeletal iron catalyst is 5-40% in the described Fischer-Tropsch synthesis process.
- 20. Fischer-Tropsch synthesis method as claimed in claim 15, it is characterized in that described Fischer-Tropsch synthesis carries out mutually in the slurry attitude, also comprise discharging gaseous hydrocarbons product and contain the liquefied hydrocarbon product of used skeletal iron catalyst, and the latter is carried out settlement separate so that catalyzer and product are separated.
- 21. Fischer-Tropsch synthesis method as claimed in claim 15, it is characterized in that using the described auxiliary agent skeletal iron catalyst that contains of claim 2 in step 1), described method comprises that also the liquefied hydrocarbon product to comprising granules of catalyst carries out settlement separate step, separates catalyzer and product.
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| WO2009094935A1 (en) * | 2008-01-23 | 2009-08-06 | Accelergy Shanghai R & D Center Co., Ltd. | Fe/mn catalyst for fischer-tropsch synthesis and its preparation method |
| WO2009100663A1 (en) * | 2008-01-23 | 2009-08-20 | Accelergy Shanghai R & D Center Co., Ltd. | Iron-based fischer-tropsch catalyst and method for making the same |
| CN100594060C (en) * | 2004-06-24 | 2010-03-17 | 青岛金王应用化学股份有限公司 | Catalyst for preparing pyroparaffine from synthesis gas and preparation method thereof |
| CN101809123A (en) * | 2007-08-10 | 2010-08-18 | Sasol技术股份有限公司 | A hydrocarbon synthesis process |
| CN101602000B (en) * | 2009-07-15 | 2011-10-05 | 神华集团有限责任公司 | Iron catalyst containing cobalt auxiliary agent for Fischer-Tropsch synthesis reaction and preparation method thereof |
| CN101164693B (en) * | 2006-10-20 | 2012-01-25 | 中国石油化工股份有限公司 | Iron catalyst, preparation method and its application in synthesizing hydrocarbon reaction |
| CN101191066B (en) * | 2006-11-30 | 2012-12-12 | 中国石油化工股份有限公司 | Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6777452B2 (en) * | 1999-09-21 | 2004-08-17 | Hydrocarbon Technologies | Promoted skeletal iron catalysts for Fischer-Tropsch synthesis processes |
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| CN101164693B (en) * | 2006-10-20 | 2012-01-25 | 中国石油化工股份有限公司 | Iron catalyst, preparation method and its application in synthesizing hydrocarbon reaction |
| CN101191066B (en) * | 2006-11-30 | 2012-12-12 | 中国石油化工股份有限公司 | Iron catalyst for preparing hydrocarbon from synthetic gas and preparation method thereof |
| 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 |
| WO2009094935A1 (en) * | 2008-01-23 | 2009-08-06 | Accelergy Shanghai R & D Center Co., Ltd. | Fe/mn catalyst for fischer-tropsch synthesis and its preparation method |
| WO2009100663A1 (en) * | 2008-01-23 | 2009-08-20 | Accelergy Shanghai R & D Center Co., Ltd. | Iron-based fischer-tropsch catalyst and method for making the same |
| CN101602000B (en) * | 2009-07-15 | 2011-10-05 | 神华集团有限责任公司 | Iron catalyst containing cobalt auxiliary agent for Fischer-Tropsch synthesis reaction and preparation method thereof |
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