CN102039135B - Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof - Google Patents

Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof Download PDF

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CN102039135B
CN102039135B CN2009102016198A CN200910201619A CN102039135B CN 102039135 B CN102039135 B CN 102039135B CN 2009102016198 A CN2009102016198 A CN 2009102016198A CN 200910201619 A CN200910201619 A CN 200910201619A CN 102039135 B CN102039135 B CN 102039135B
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tropsch
fluidized bed
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CN102039135A (en
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庞颖聪
陶跃武
郭宗英
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof. The invention is aimed to solve the problems in the prior art that because Fischer-Tropsch synthesis is a strongly exothermic reaction, when a fixed bed is used, heat dissipation in the reactor is difficult and temperature jump is easy to occur in the reaction so as to allow an easy inactivation of the catalyst; when a fluidized bed is used, reaction temperature is high and the selectivity of ingredients of gasoline and diesel oil is relatively low. The catalyst of the invention is composed of at least one oxide selected from oxides of Si or Al as a carrier, and an active component comprising the composition of the chemical formula in terms of atomic ratio: Fe100AaBbCcDdOx, wherein A is selected from at least one of alkali metals or alkaline earth metals; B is selected from at least one of La or Ce; C is selected from at least one of Cu or Mn; D is selected from at least one of Co or Ni. The catalyst is applicable to the industrial production of Fischer-Tropsch synthesis.

Description

Fe-based fluidized bed catalyst for Fischer-Tropsch and preparation method thereof
Technical field
The present invention relates to a kind of Fe-based fluidized bed catalyst for Fischer-Tropsch and preparation method thereof.
Background technology
The method that synthesis gas process catalyst action is converted into liquid hydrocarbon is that nineteen twenty-three is by Germany scientist Frans Fischer and Hans Tropsch invention, be called for short F-T synthetic, being CO at metallic catalyst the heterogeneous catalysis hydrogenation occurs, and generates the process take linear paraffin and alkene as main mixture.Germany has just carried out research and development in the twenties in last century, and has realized industrialization in 1936, after World War II because closing with the petroleum industry competition economically; South Africa has abundant coal resources, but the petroleum resources plaque is weary, and be subject to for a long time the restriction of international community's economy and political sanction, force its Development of Coal oils preparation industry technology, and to have built up First production capacity in 1955 be the coal-based F-T artificial oil factory (Sasol-1) in 25～400,000 tons of product/years.
Currently reported ferrum-based catalyst is divided into two kinds of precipitated iron and molten irons: precipitated iron catalyst wherein is multiplex produces high-carbon hydrocarbon and wax on fixed bed and slurry attitude bed, be used for industrial precipitated iron FTS catalyst such as Sasol, Chinese Academy of Sciences's coalification a kind of microspheroidal Fischer-Tropsch synthetic iron-based catalyst of in patent CN1395992A, applying for, the high-carbon hydrocarbon of gained need to just can change vapour, diesel oil and other chemical products into through deep processing, has increased production cost and complex process degree; Be used for the fused iron catalysts that mostly is that fluid bed is directly produced light hydrocarbon, a kind of for the synthetic molten iron type catalyst of high temperature fischer-tropsch as just having mentioned among the patent CN1704161A, but this method for preparing catalyst needs high temperature, high pressure and energy consumption high.In patent CN1695804A, mentioned a kind of precipitated iron catalyst for fluid bed, but precipitation method complicated process of preparation, the required cycle is long.
Summary of the invention
One of technical problem to be solved by this invention be exist in the prior art because Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, the heat difficulty is removed in reaction, easily temperature runaway makes the easy inactivation of catalyst; When using fluid bed, selective low problem provides a kind of new synthetic iron-based fluid catalyst of Fischer-Tropsch that is used for.This catalyst has high-temperature fluidized bed device operation in being applicable to and being not limited to, and mechanical strength is strong, and wear rate is low, the advantage that cost is low.Two of technical problem to be solved by this invention provides the preparation method of the required catalyst-compatible of one of a kind of and technical solution problem.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of Fe-based fluidized bed catalyst for Fischer-Tropsch, at least a as carrier in the oxide that is selected from Si or Al, active component contains with the following composition of atomic ratio measuring chemical formula:
Fe 100A aB bC cD dO x
A is selected from least a in alkali metal or the alkaline-earth metal in the formula;
B is selected from least a among La or the Ce;
C is selected from least a among Cu or the Mn;
D is selected from least a among Co or the Ni;
The span of a is 0.1～10.0;
The span of b is 0～10.0; When C is Mn, b＞0;
The span of c is 5.0～60.0;
The span of d is 0.1～15.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
The carrier consumption is 30～70% of catalyst weight by weight percentage.
In the technique scheme, the value preferable range of a is 1.0～8.0; The value preferable range of b is 0.1～8.0; The value preferable range of c is 10～50; The value preferable range of d is 1.0～10.0; Carrier consumption preferable range is 40～60% of catalyst weight by weight percentage.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of Fe-based fluidized bed catalyst for Fischer-Tropsch may further comprise the steps:
(1) soluble ferric iron salt is dissolved in water makes solution I;
(2) with solubility B, C, solution II is made in the dissolving soluble in water of the salt of D;
(3) solution I and II are mixed and made into mixed solution I II;
(4) in hot bath, will be selected from SiO 2Or Al 2O 3In at least a colloidal sol and the hydroxide of A join in the solution III, mix making beating, add simultaneously acid-base modifier and regulate the PH of slurry and 0.1～7 obtain slurry IV;
(5) send into the spray dryer spray shaping after slurry IV is cooled to 40～60 ℃, then roasting 0.15～6 hour under 400～750 ℃ of conditions obtains the synthetic fluid catalyst of microsphere shaped iron based Fischer-Tropsch.
In the technique scheme, the solid content preferable range of described catalyst pulp IV is 15～45wt%; The pH value preferable range of described catalyst pulp IV is 1～5; The spray shaping condition of described catalyst is that the inlet temperature preferable range is 200～360 ℃, and the outlet temperature preferable range is 100～210 ℃; The sintering temperature preferable range of described catalyst is 450～700 ℃; The roasting time preferable range of described catalyst is 0.5～5h.
The catalyst that the inventive method makes becomes microspheroidal, and granularity concentrates on 30～100 μ m, and mechanical strength is strong, and wear rate is low, meets the requirement of Fluidized Multicomponent Metallic Oxides Catalysts, is applicable to the fluid bed high temperature fischer-tropsch synthetic, and yield rate reaches more than 95%.
The catalyst particle size of the prepared microspherical iron-based catalyst of the inventive method distributes and adopts laser fineness gage to measure.
Because the fluid catalyst that the inventive method makes can be used in fluidized-bed process, therefore solved in the prior art because Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, reactor is removed the heat difficulty, easy temperature runaway makes the problem of the easy inactivation of catalyst; In addition owing in catalyst, introducing rare earth element as catalyst promoter, promoted the dispersion of catalyst activity component at catalyst surface, thereby be conducive to improve the activity of catalyst, make it can under middle high temperature, keep preferably conversion ratio and selective, solved when using fluid bed, must carry out under the high temperature, and the selective low problem of gasoline, diesel component.Because the present invention adopts directly the spray-dired method of prepared slurry, save precipitation, washing and beating process process in addition in catalyst preparation process, simplified technique, reduced energy consumption.This catalyst is aspect Fischer-Tropsch synthesizing low-carbon alkene and gasoline, diesel, and its CO conversion ratio can reach 91%, C 5～C 18Selectively can reach 56%, carbon five and above hydrocarbon (C 5 +) selectively can reach 72%, obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
306.1 gram ferric nitrates are dissolved in 300 grams are made into certain density solution I in 90 ℃ of water; With 90.59 gram copper nitrates, 17.6 gram nickel nitrates, 10.9 gram lanthanum nitrates are dissolved in wiring solution-forming II in 90 ℃ of water of 200 grams; Solution I, II are mixed to get solution III; Place boiling water bath to heat solution III, add simultaneously 375.0 gram weight concentration and be 40% Ludox and 1.02 gram potassium hydroxide/5 gram aqueous solution making beating, then the pH value with ammoniacal liquor adjusting slurry is 5, after fully stirring, obtain required catalyst pulp (solid content 15%), with this slurry spray drying forming, the spraying machine inlet temperature is 360 ℃, 210 ℃ of outlet temperatures, then carry out roasting, 750 ℃ of sintering temperatures, roasting time 6 hours obtains microsphere shaped iron based fischer-tropsch synthetic catalyst, and it is made and consists of:
40％Fe 100K 2.0La 5.0Cu 50.0Ni 8.0O x+60％SiO 2
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 2～7]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst that form, gained catalyst numbering and composition are respectively:
Embodiment 2 50%Fe 100K 5.0La 1.0Ce 4.0Cu 18.0Co 2.0O x+ 50%Al 2O 3(the slurry pH value is 0.1; Solid content 45%; Spray condition: 200 ℃ of imports export 100 ℃; 600 ℃ of sintering temperatures, 0.15 hour time)
Embodiment 3 55%Fe 100K 1.5Ca 4.0La 1.8Mn 30.0Co 5.0O x+ 55%SiO 2(the slurry pH value is 3; Solid content 35%; Spray condition: 230 ℃ of imports export 140 ℃; 400 ℃ of sintering temperatures, 4 hours time)
Embodiment 4 60%Fe 100Mg 6.0Ce 7.0Cu 25.0Ni 2.5Co 2.50O x+ 40% (50%SiO 2+ 50%Al 2O 3) (the slurry pH value is 2.5; Solid content 30%; Spray condition: 280 ℃ of imports export 150 ℃; 550 ℃ of sintering temperatures, time 2 h)
Embodiment 5 45%Fe 100Mg 1.0Ca 7.0La 3.0Cu 10.0Mn 40.0Ni 1.0O x+ 55%SiO 2(the slurry pH value is 3.7; Solid content 25%; Spray condition: 320 ℃ of imports export 160 ℃; 450 ℃ of sintering temperatures, 1 hour time)
Embodiment 6 60%Fe 100Na 1.0Sr 5.0La 1.0Cu 38.0Co 6.0O x+ 40%SiO 2(the slurry pH value is 3.1; Solid content 20%; Spray condition: 250 ℃ of imports export 135 ℃; 650 ℃ of sintering temperatures, 3.5 hours time)
Embodiment 7 50%Fe 100Na 4.0K 4.0Ce 0.5Cu 20.0Co 6.0Ni 4.0O x+ 50%SiO 2(the slurry pH value is 7; Solid content 35%; Spray condition: 230 ℃ of imports export 130 ℃; 600 ℃ of sintering temperatures, 1.5 hours time)
Prepared catalyst carries out Fischer-Tropsch synthesis under following reaction condition, the results are shown in Table 1.
[comparative example 1～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyst that form, gained catalyst numbering and composition are respectively:
Comparative example 1 40%Fe 100La 8.0Cu 40.0Co 3.0O x+ 60%SiO 2(the slurry pH value is 5; Solid content 20%; Spray condition: 250 ℃ of imports export 135 ℃; 650 ℃ of sintering temperatures, 3.5 hours time)
Comparative example 2 50%Fe 100K 2.0Mn 30.0Ni 2.0O x+ 50%SiO 2(the slurry pH value is 4.3; Solid content 35%; Spray condition: 230 ℃ of imports export 130 ℃; 600 ℃ of sintering temperatures, 1.5 hours time)
Comparative example 3 55%Fe 100K 4.0La 5.0Co 7.0O x+ 50%SiO 2(the slurry pH value is 2.5; Solid content 30%; Spray condition: 280 ℃ of imports export 150 ℃; 550 ℃ of sintering temperatures, time 2 h)
Comparative example 4 60%Fe 100K 8.0La 1.0Cu 50.0O x+ 50%SiO 2(the slurry pH value is 1; Solid content 15%; Spray condition: 360 ℃ of imports export 210 ℃; 700 ℃ of sintering temperatures, 6 hours time)
Prepared catalyst carries out Fischer-Tropsch synthesis under following reaction condition, the result also lists in table 1.
The reducing condition of above-described embodiment and comparative example is:
400 ℃ of temperature
Pressure 3.0MPa
Loaded catalyst 100 grams
Catalyst loading 4000 hours -1
Reducing gases H 2/ CO=2/1
24 hours recovery times
Reaction condition is:
Figure G2009102016198D00051
The millimeter fluidized-bed reactor
280 ℃ of reaction temperatures
Reaction pressure 2.0MPa
Loaded catalyst 100 grams
Catalyst loading 3000 hours -1
Raw material proportioning (mole) H 2/ CO=2/1
The evaluation result of table 1 embodiment catalyst
Figure G2009102016198D00052

Claims (7)

1. Fe-based fluidized bed catalyst for Fischer-Tropsch, at least a as carrier in the oxide that is selected from Si or Al, active component contains with the following composition of atomic ratio measuring chemical formula:
Fe 100A aB bC cD dO x
A is selected from least a in alkali metal or the alkaline-earth metal in the formula;
B is selected from least a among La or the Ce;
C is selected from least a among Cu or the Mn;
D is selected from least a among Co or the Ni;
The span of a is 0.1～10.0;
The span of b is 0～10.0; When C is Mn, b＞0;
The span of c is 5.0～60.0;
The span of d is 0.1～15.0;
X satisfies the required oxygen atom sum of each element valence in the catalyst;
The carrier consumption is 30～70% of catalyst weight by weight percentage;
The preparation method of described Fe-based fluidized bed catalyst for Fischer-Tropsch may further comprise the steps:
(1) soluble ferric iron salt is dissolved in water makes solution I;
(2) with solubility B, C, solution II is made in the dissolving soluble in water of the salt of D;
(3) solution I and II are mixed and made into mixed solution I II;
(4) in hot bath, will be selected from SiO 2Or Al 2O 3In at least a colloidal sol and the hydroxide of A join in the solution III, mix making beating, add simultaneously acid-base modifier and regulate the pH of slurry and 0.1～7 obtain slurry IV;
(5) send into the spray dryer spray shaping after slurry IV is cooled to 40～60 ℃, then roasting 0.15～6 hour under 400～750 ℃ of conditions obtains the synthetic fluid catalyst of microsphere shaped iron based Fischer-Tropsch.
2. described Fe-based fluidized bed catalyst for Fischer-Tropsch according to claim 1, the span that it is characterized in that a is 1.0～8.0; The span of b is 0.1～8.0; The span of c is 10～50; The span of d is 1.0～10.0; The carrier consumption is 40～60% of catalyst weight by weight percentage.
3. the preparation method of Fe-based fluidized bed catalyst for Fischer-Tropsch claimed in claim 1 may further comprise the steps:
(1) soluble ferric iron salt is dissolved in water makes solution I;
(2) with solubility B, C, solution II is made in the dissolving soluble in water of the salt of D;
(3) solution I and II are mixed and made into mixed solution I II;
(4) in hot bath, will be selected from SiO 2Or Al 2O 3In at least a colloidal sol and the hydroxide of A join in the solution III, mix making beating, add simultaneously acid-base modifier and regulate the pH of slurry and 0.1～7 obtain slurry IV;
(5) slurry IV is cooled to 40～60.Send into the spray dryer spray shaping after ℃, then roasting 0.15～6 hour under 400～750 ℃ of conditions obtains the synthetic fluid catalyst of microsphere shaped iron based Fischer-Tropsch.
4. the preparation method of described Fe-based fluidized bed catalyst for Fischer-Tropsch according to claim 3, the pH value that it is characterized in that described slurry IV is 1～5.
5. the preparation method of described Fe-based fluidized bed catalyst for Fischer-Tropsch according to claim 3, the solid content that it is characterized in that described slurry IV is 15～45wt%.
6. the preparation method of described Fe-based fluidized bed catalyst for Fischer-Tropsch according to claim 3 is characterized in that spray-dired inlet temperature is 200～360 ℃, and outlet temperature is 100～210 ℃.
7. the preparation method of described Fe-based fluidized bed catalyst for Fischer-Tropsch according to claim 3 is characterized in that sintering temperature is 450～700 ℃, and roasting time is 0.5～5 hour.
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CN103657676B (en) * 2012-09-05 2016-04-13 中国石油化工股份有限公司 Microspherical Fischer-Tropsch catalyst and its preparation method and application
CN104549343B (en) * 2013-10-28 2017-07-14 中国石油化工股份有限公司 Preparation of low carbon olefines by synthetic gas catalyst, preparation method and its usage
CN111068703A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof
CN111068690A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof
CN112705218B (en) * 2019-10-24 2023-11-28 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof

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