CN103521238B - Micro spherical Fischer-Tropsch synthesis catalyst and preparation method thereof - Google Patents
Micro spherical Fischer-Tropsch synthesis catalyst and preparation method thereof Download PDFInfo
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- CN103521238B CN103521238B CN201210225875.2A CN201210225875A CN103521238B CN 103521238 B CN103521238 B CN 103521238B CN 201210225875 A CN201210225875 A CN 201210225875A CN 103521238 B CN103521238 B CN 103521238B
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Abstract
The invention relates to a heavy hydrocarbon Fischer-Tropsch synthesis catalyst and a preparation method thereof. Since a Fischer-Tropsch synthesis reaction is a strong exothermic reaction, when a fixed bed is used, reaction heat is difficult to remove, temperature runaway is easily caused and a catalyst is easily inactivated and when a fluidized bed is used, selectivity of heavy hydrocarbon (hydrocarbons containing more than five carbon atoms) is low. By adoption fo the heavy hydrocarbon Fischer-Tropsch synthesis catalyst and the preparation method thereof, provided by the invention, all the problems in the prior art can be solved. According to the technical scheme, an iron-based fluidized bed catalyst is adopted, wherein at least one of Si and Al oxides is taken as a carrier of the catalyst and the active component of the catalyst contains a composition with the following chemical formula in atomic ratio: Fe100AaMnbCrcOx; and synthetic gas serving as raw material comes into contact with the iron-based fluidized bed catalyst in a fluidized bed to react under the conditions that the reaction pressure is 0.5-10MPa, the reaction temperature is 200-600 DEG C, reaction air speed is 100-8000/h and ratio of H2/CO in the raw material gas is (0.1-5.0):1, so as to generate heavy hydrocarbon. The heavy hydrocarbon Fischer-Tropsch synthesis catalyst can be applied to industrial production of fluidized bed Fischer-Tropsch synthesis reaction.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of Fischer-Tropsch synthesis of heavy hydrocarbon.
Background technology
The method that synthesis gas is converted into liquid hydrocarbon through catalyst action is invented by Germany scientist Frans Fischer and Hans Tropsch nineteen twenty-three, be called for short F-T synthesis, namely there is heterogeneous catalysis hydrogenation in CO on metallic catalyst, generates based on the process of the mixture of linear paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and achieves industrialization in 1936, closes after World War II because competing with petroleum industry economically; South Africa has abundant coal resources, but petroleum resources plaque is weary, and be subject to the restriction of international community's economy and political sanction for a long time, force its Development of Coal oils preparation industry technology, and built up in 1955 the coal-based F-T artificial oil factory (Sasol-1) that First production capacity is ten thousand tons of product/years of 25-40.
Twice world oil crisis of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, based on the consideration of Strategic Technology deposit, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol company builds up again and two coal-based artificial oil factories of having gone into operation in succession.But plummeting of World oil price in 1986, has postponed the heavy industrialization process of F-T synthetic technology in other country.
Since twentieth century nineties, petroleum resources are shortage and in poor quality increasingly, and coal and natural gas proved reserves but constantly increase simultaneously, and GTL technology causes extensive concern again.Through the development of decades, Fischer-Tropsch catalyst have also been obtained significant progress, and catalyst conventional at present, is divided into two large classes: ferrum-based catalyst and cobalt-base catalyst active component.According to the difference of adopted catalyst and the difference of target product, Fischer-Tropsch synthesis device is divided into again fixed bed reactors, fluidized-bed reactor and paste state bed reactor.Fixed bed reactors complex structure, expensive, remove heat difficulty, the production capacity of whole device is lower.The feature of slurry bed system is that reaction temperature is lower, is easy to control, but conversion ratio is lower, product mostly be high-carbon hydrocarbon and in reactor the solid-liquor separation of slurries comparatively difficult.The feature of fluidized-bed reactor is that temperature is higher, and conversion ratio is higher, and there is not the difficulty of solid-liquor separation, product mostly is lower carbon number hydrocarbons; Build and operating cost lower, and low pressure reduction in turn saves a large amount of compression expenses, and is more conducive to the heat of releasing in dereaction, and simultaneously because gas linear velocity is low, wear problem is less, and this makes to operate for a long time to become possibility.
Iron catalyst has a lot of advantages, as highly selective obtains low-carbon alkene, prepares high-octane gasoline etc., and ferrum-based catalyst also has the feature that operating condition is wide, product adjustability is large in addition.The preparation method of Fe-series catalyst mainly contains three kinds: the precipitation method (precipitated catalyst), sintering process (sintered catalyst) and oxide mixing method (fused iron catalyst).The currently reported molten iron type that the mostly is catalyst being applied to fluid bed F-T synthesis, as being referred to a kind of molten iron type catalyst for F-T synthesis in patent CN1704161A, catalyst by Fe, Al, K, Ca oxide and on a small quantity other oxide form, reaction temperature 280 DEG C, reaction pressure 6.0MPa, catalyst loading 500 hours
-1, pulp furnish (mole) H
2under the condition of/CO=1.5, CO conversion ratio is the selective of 93.4%, C5+ hydrocarbon is 60.2%.But be that molten iron method Kaolinite Preparation of Catalyst or the precipitation method are prepared Fluidized Multicomponent Metallic Oxides Catalysts and all be there is complex process, energy consumption is high, the shortcoming that the catalyst preparing cycle is long.
Summary of the invention
One of technical problem to be solved by this invention is because the Fischer-Tropsch synthesis existed is strong exothermal reaction in prior art, and when using fixed bed, heat difficulty is removed in reaction, and easy temperature runaway, makes the easy inactivation of catalyst; When using fluid bed, the selective low problem of heavy hydrocarbon, provides a kind of ferrum-based catalyst of new Fischer-Tropsch synthesis of heavy hydrocarbon.This catalyst has the fluidized-bed reactor being applicable to and being not limited to middle high temperature, the selective high advantage of heavy hydrocarbon.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the catalyst-compatible required with one of technical solution problem.
As follows for solving the problems of the technologies described above a technical solution used in the present invention: a kind of ferrum-based catalyst of Fischer-Tropsch synthesis of heavy hydrocarbon.This catalyst is to be selected from least one of the oxide of Si or Al for carrier, and active component contains with atomic ratio measuring, the composition that chemical formula is following:
Fe
100A
aMn
bCr
cO
x
In formula, A is selected from alkali-metal at least one;
The span of a is 0.1 ~ 15.0;
The span of b is 5.0 ~ 60.0;
The span of c is 0. 1 ~ 15.0;
X is for meeting the oxygen atom sum in catalyst needed for each element valence;
Carrier consumption is 30 ~ 70% of catalyst weight by weight percentage.
In technique scheme, the value preferable range of the value preferable range of a to be the value preferable range of 1.0 ~ 10.0, b be 10.0 ~ 50.0, c is 1.0 ~ 10.0, and carrier consumption preferable range is 40 ~ 60% of catalyst weight by weight percentage.
As follows for solving the problems of the technologies described above two the technical solution used in the present invention: the preparation method of the ferrum-based catalyst of Fischer-Tropsch synthesis of heavy hydrocarbon, comprise following processing step:
(1) solution I is made by soluble in water for aequum soluble ferric iron salt,
(2) by the salt of aequum solubility A or oxide or hydroxide is soluble in water makes solution II,
(3) by the soluble-salt of aequum Cr or oxide is soluble in water makes solution III,
(4) soluble-salt of solution I solution and Mn is mixed and made into mixed solution IV,
(5) in 70-100 DEG C of water-bath, aequum is selected from SiO
2or Al
2o
3in the colloidal sol of at least one and solution II, III join in solution IV, mixing making beating, add acid-base modifier simultaneously and regulate the pH value of slurry to be 1 ~ 5, obtaining solid content is 15 ~ 45wt% slurry V,
(6) send into spray dryer spray shaping after slurry V being cooled to 20 ~ 60 DEG C, then 400 ~ 750 DEG C of roasting temperatures 0.15 ~ 6 hour, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst.
The manufacture method of the catalyst in the inventive method there is no particular/special requirement, can be undertaken by well-established law.First catalyst each component is made solution, then be mixed and made into slurry with carrier, be spray-driedly shaped to microspheroidal, finally make catalyst at 450-700 DEG C of roasting 0.5-5 hour.The preparation of slurry is preferably undertaken by CN1005248C method.
The raw material manufacturing catalyst of the present invention is:
Iron component ferric nitrate in catalyst or ferric sulfate.
All the other components its nitrate the most handy, hydroxide or can be analyzed to the salt of oxide.
Raw material as carrier silicas can use Ludox, Silica hydrogel or both mixtures.If with Ludox, its quality will meet the requirement of CN1005248C.
Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but with better centrifugal, can ensure that the catalyst made has good size distribution.
The roasting of catalyst can be divided into two stages to carry out: the decomposition of each element salt and high-temperature roasting in catalyst.Catabolic phase temperature is preferably 200 ~ 300 DEG C, and the time is 0.5 ~ 2 hour.Sintering temperature is 500 ~ 800 DEG C, is preferably 550 ~ 700 DEG C; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two regions in a stove, in continous way rotary roasting furnace, also can complete decomposition and roasting simultaneously.Appropriate air to be passed into, to generate Catalytic active phase in catalyst decomposes and roasting process.
The reducing condition of the catalyst that the present invention obtains: pressure is between 0.05 ~ 5MPa, is preferably 0.1 ~ 4MPa; Reducing gas can use hydrogen, carbon monoxide or synthesis gas, when using synthesis gas, and its H
2/ CO mol ratio is 0.1 ~ 6.0, is preferably 0.2 ~ 6.0; The load of reducing gases is 100 ~ 8000 hours
-1, be preferably 500 ~ 6000 hours
-1; Reduction temperature is 200 ~ 600 DEG C, is preferably 220 ~ 500 DEG C; Recovery time is 1 ~ 100 hour, is preferably 6 ~ 72 hours.
The reaction condition of the catalyst that the present invention obtains: pressure is between 0.5 ~ 10MPa, is preferably 1 ~ 8MPa; Reaction temperature is 200 ~ 600 DEG C, is preferably 220 ~ 500 DEG C; Catalyst loading is 100 ~ 8000 hours
-1, be preferably 500 ~ 6000 hours
-1; H in unstripped gas
2/ CO mol ratio is 0.1 ~ 5.0, is preferably 0.5 ~ 3.0.
Because the present invention adopts fluidized-bed process, therefore solve because Fischer-Tropsch synthesis is strong exothermal reaction in prior art, when using fixed bed, heat difficulty is removed in reaction, and easy temperature runaway, makes the problem of the easy inactivation of catalyst; In addition due to introduce in the catalyst manganese, chromium as catalyst promoter, facilitating the dispersion of catalyst activity component at catalyst surface, thus be conducive to improving the activity of catalyst, solving when using fluid bed, the selective low problem of heavy hydrocarbon.Use method of the present invention, reaction temperature 200 ~ 600 DEG C, reaction pressure 0.5 ~ 10MPa, catalyst loading 100 ~ 8000 hours
-1, pulp furnish (mole) H
2carry out Fischer-Tropsch synthesis under the condition of/CO=0.1 ~ 5.0:1, CO conversion ratio can reach 91.2%, and in product, the selective of heavy hydrocarbon reaches 70.8%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
The present invention is described further for the following examples, and protection scope of the present invention is not by the restriction of these embodiments.
[embodiment 1]
424.2 grams of ferric nitrates are added water 500 grams and dissolves, obtain material (I), 3.52 grams of potassium hydroxide add water 10 grams of heating for dissolving, obtain material (II), 5.25 grams of chromium trioxides add 10 grams of water, stirring and dissolving obtains material (III), adds 184.1 grams of manganese nitrates and obtain material (IV) in material (I).
Under agitation in material (IV), add the Ludox material that 625 gram weight concentration are 40%, and then slowly add material (II), material (III); The acidity of above-mentioned slurry is regulated to make the pH=6.0 of mixed slurry with ammoniacal liquor, slurry is obtained after fully stirring, the slurry made carried out in spray dryer framboid according to well-established law shaping, last is 89 millimeters at internal diameter, length be in the rotary roasting furnace of 1700 millimeters (φ 89 × 1700 millimeters) in 500 DEG C of roastings 2.0 hours, make and consist of:
50% Fe
100K
5.0Mn
50.0Cr
5.0O
x＋50%SiO
2。
Catalyst.
Obtained catalyst carries out at reducing condition:
Temperature 400 DEG C
Pressure 3.0MPa
Loaded catalyst 100 grams
Catalyst loading 4000 hours
-1
Reducing gases H
2/ CO=2/1
24 hours recovery times
Reduce, then carry out Fischer-Tropsch synthesis under the following conditions:
φ 38 millimeters of fluidized-bed reactors
Reaction temperature 280 DEG C
Reaction pressure 2.0MPa
Loaded catalyst 100 grams
Catalyst loading 3000 hours
-1
Pulp furnish (mole) H
2/ CO=2/1
The experimental result of Fischer-Tropsch synthesis lists in table 1.
[embodiment 2 ~ 6]
Adopt method preparation substantially the same manner as Example 1 to have the catalyst of different composition, gained catalyst numbering and composition are respectively:
Embodiment 1 50% Fe
100k
5.0mn
50.0cr
5.0o
x+ 50%SiO
2
Embodiment 2 60% Fe
100li
3.0mn
10.0cr
6.5o
x+ 40%Al
2o
3
Embodiment 3 45% Fe
100na
8.5mn
25.0cr
10.0o
x+ 55%SiO
2
Embodiment 4 50% Fe
100cs
6.0mn
40.0cr
1.0o
x+ 50% (50%SiO
2+ 50%Al
2o
3)
Embodiment 5 40% Fe
100k
0.5cs
0.5mn
30.0cr
2.5o
x+ 60%SiO
2
Embodiment 6 55% Fe
100k
5.0na
5.0mn
20.0cr
8.0o
x+ 45%SiO
2
Obtained catalyst carries out Fischer-Tropsch synthesis under following reaction condition, the results are shown in Table 1.
[comparative example 1 ~ 3]
Adopt method preparation substantially the same manner as Example 1 to have the catalyst of different composition, gained catalyst numbering and composition are respectively:
Comparative example 1 50% Fe
100mn
25.0cr
5.0o
x+ 50%SiO
2
Comparative example 2 50% Fe
100k
5.0cr
5.0o
x+ 50%SiO
2
Comparative example 3 50% Fe
100k
0.5mn
30.0o
x+ 50%SiO
2
Obtained catalyst carries out Fischer-Tropsch synthesis under following reaction condition, and result also lists in table 1.
The evaluation result of table 1 embodiment catalyst
[embodiment 7]
By each step and the condition Preparation and evaluation catalyst of embodiment 1, just reaction temperature is 250 DEG C, and its appreciation condition lists in table 2, and evaluation result lists in table 3.
[embodiment 8-14]
By each step and the condition Preparation and evaluation catalyst of embodiment 1, just change a certain appreciation condition wherein, its appreciation condition lists in table 2, and evaluation result lists in table 3.
The appreciation condition of table 2 embodiment 7-14
The evaluation result of catalyst under table 3 different evaluation condition
Claims (1)
1. the method for a Fischer-Tropsch synthesis of heavy hydrocarbon, 424.2 grams of ferric nitrates are added water 500 grams and dissolves, obtain material (I), 3.52 grams of potassium hydroxide add water 10 grams of heating for dissolving, obtain material (II), 5.25 grams of chromium trioxides add 10 grams of water, and stirring and dissolving obtains material (III), add 184.1 grams of manganese nitrates and obtain material (IV) in material (I); Under agitation in material (IV), add the Ludox material that 625 gram weight concentration are 40%, and then slowly add material (II), material (III) obtains slurry; The acidity of above-mentioned slurry is regulated to make the pH=6.0 of mixed slurry with ammoniacal liquor, slurry is obtained after fully stirring, the slurry made is carried out in spray dryer framboid shaping, last is 89 millimeters at internal diameter, length be in the rotary roasting furnace of 1700 millimeters in 500 DEG C of roastings 2.0 hours, make and consist of: 50%Fe
100k
5.0mn
50.0cr
5.0o
x+ 50%SiO
2catalyst;
Obtained catalyst carries out at reducing condition:
Temperature 400 DEG C
Pressure 3.0MPa
Loaded catalyst 100 grams
Catalyst loading 4000 hours
-1
Reducing gases H
2/ CO=2/1
24 hours recovery times
Reduce, then carry out Fischer-Tropsch synthesis under the following conditions:
millimeter fluidized-bed reactor
Reaction temperature 280 DEG C
Reaction pressure 2.0MPa
Loaded catalyst 100 grams
Catalyst loading 3000 hours
-1
Pulp furnish (mole) H
2/ CO=2/1
It is 92.1%, CH that the experimental result of Fischer-Tropsch synthesis shows its CO conversion ratio
4selective be 10.3wt%, C
2~ C
4selective is 18.0wt%, C
5~ C
18selective is 53.7wt%, C
19 +selective is 17.3wt%, and oxygen-bearing organic matter overall selectivity is 0.7wt%.
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| CN102453492A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method for heavy hydrocarbons |
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