CN102371154B - Iron-based catalyst for synthesizing light hydrocarbon and preparation method thereof - Google Patents
Iron-based catalyst for synthesizing light hydrocarbon and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an iron-based catalyst for synthesizing light hydrocarbon and a preparation method thereof, mainly solving the problems of difficult heat removing and easy temperature runaway in the reactor and easy inactivation of the catalyst when using static bed, and high reaction temperature and relatively low selectivity of gasoline and diesel fuels when using fluidized bed in the prior art because the Fischer-Tropsch synthesis is a strong exothermic reaction. The catalyst comprises at least one of oxides of Si or Al as the carrier and an active ingredient which is measured as atomic ratio and represented by Fe100AaBbCcOx, wherein, A is at least one selected from the group consisting of V and Nb, B is one selected from the group consisting of Cu and Zn, and C is at least one selected from alkali metal. The catalyst can be used in but not limited to medium and high temperature fluidized bed reactors.
Description
Technical field
The present invention relates to ferrum-based catalyst of the synthetic light hydrocarbon of a kind of Fischer-Tropsch and preparation method thereof.
Background technology
Along with the fast development of China's economy, be to grow with each passing day to the demand of low-carbon alkene and liquid fuel.The characteristics of China's energy are that the few oil of rich coal has gas, and the environmental pollution that the direct burning of coal causes also comes into one's own increasingly.Exploitation is converted into the process of low-carbon alkene and liquid fuel by coal/natural gas via synthesis gas, not only can reduce on the energy external dependence, and have great importance for solving the coal-fired problem of environmental pollution that causes.
Fischer-Tropsch (Fascher-Tropsch) is synthetic is to utilize synthesis gas (main component is CO and H
2) process of synthetic hydrocarbon under the effect of catalyst, be an important channel of coal and natural gas indirect liquefaction.
The cryogenic high pressure paste state bed reactor that is applicable to that the fischer-tropsch catalysts of document and patent report is many is in recent years produced high-carbon long-chain olefin type, generally mostly is precipitated iron catalyst, or the immersion-type Co catalysts.Just reported a kind of preparation method who is applicable to the synthetic precipitated iron catalyst of Fischer-Tropsch of paste state bed reactor as U.S. Rentech company in patent USP5504118 and CN1113905A---first with active component precipitation, filtration and washing, and then mix, pull an oar with carrier, last spray-drying.Precipitation, filtration and washing step in the method Kaolinite Preparation of Catalyst process are loaded down with trivial details, operation inconvenience, and energy consumption is high.
Synthetic general how the carrying out in fluidized-bed reactor of the Fischer-Tropsch of light hydrocarbon, the characteristics of this technique are that reaction temperature is higher, conversion ratio is higher, does not have the difficulty of liquid-solid separation.But the currently reported synthetic molten iron type that the mostly is catalyst of fluid bed Fischer-Tropsch that is applied to occasionally has the precipitated iron catalyst of some types.As just having mentioned a kind of preparation for the synthetic molten iron type catalyst of Fischer-Tropsch in patent CN1704161A, mentioned a kind of precipitated iron catalyst for fluid bed in patent CN1695804A, but be that the standby catalyst of molten iron legal system or the precipitation method prepare Fluidized Multicomponent Metallic Oxides Catalysts and all have complex process, energy consumption is high, the shortcoming that the catalyst manufacturing cycle is long.
Summary of the invention
One of technical problem to be solved by this invention be exist in prior art because Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, the heat difficulty is removed in reaction, easily temperature runaway, make the easy inactivation of catalyst; When using fluid bed, the selective low problem of petrol and diesel oil provides a kind of new Fischer-Tropsch to synthesize the ferrum-based catalyst of light hydrocarbon.This catalyst has the fluidized-bed reactor that is applicable to and is not limited to middle high temperature, low-carbon alkene and the high advantage of gasoline, diesel compositional selecting.Two of technical problem to be solved by this invention is to provide the preparation method of the required catalyst-compatible of one of a kind of and technical solution problem.
As follows for solving the problems of the technologies described above a technical solution used in the present invention: the ferrum-based catalyst of the synthetic light hydrocarbon of a kind of high temperature fischer-tropsch, this catalyst is at least a as carrier take the oxide that is selected from Si or Al, active component contains with atomic ratio measuring, the composition that chemical formula is following: Fe
100A
aB
bC
cO
x(in formula, A is selected from least a in V or Nb; B is selected from least a in Cu or Zn; C is selected from least a in alkali metal; The span of a is 5.0～60.0; The span of b is 0～20.0; The span of c is 0.1～10.0; X satisfies the required oxygen atom sum of each element valence in catalyst), the carrier consumption is 15～80% of catalyst weight by weight percentage.In technique scheme, the value preferable range of a is that the value preferable range of 10.0～50.0, b is that the value preferable range of 3.0～18.0, c is 0.2～8.0, and carrier consumption preferable range is 25～70% 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 the synthetic light hydrocarbon of Fischer-Tropsch comprises following processing step:
(1) with the aequum soluble ferric iron salt solution I of making soluble in water;
(2) in the aequum ammonium metavanadate is soluble in water or oxalic acid solution that the aequum niobium hydroxide is dissolved in or two solution are mixed and made into the solution II by a certain percentage;
(3) with the aequum solubility category-B salt solution III of making soluble in water;
(4) solution I solution, II solution, III solution mixing system are become the mixed solution IV;
(5) in boiling water bath, aequum is selected from SiO
2Or Al
2O
3In at least a colloidal sol and hydroxide or the salting liquid of C class join in the solution IV, mix making beating, the pH value that adds simultaneously acid-base modifier to regulate slurry is 1～5 to obtain the slurry V (solid content is 15～45wt%);
(6) send into the spray dryer spray shaping after the slurry V is cooled to 20～60 ℃, then 400～750 ℃ of roasting temperatures 0.15～6 hour, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst.
The spray shaping condition of described catalyst is 200～360 ℃ of inlet temperatures, 100～210 ℃ of outlet temperatures.
Best 450～700 ℃ of the sintering temperature of described catalyst;
The roasting time of described catalyst is preferably 0.5～5h;
The catalyst that according to said method obtains is carried out Fischer-Tropsch synthesis under suitable reaction condition, obtained technique effect (the results are shown in subordinate list) preferably.
The present invention is described further for the following examples, and protection scope of the present invention is not subjected to the restriction of these embodiment.
The specific embodiment
[embodiment 1]
getting a certain amount of ferric nitrate is dissolved in the water and is made into certain density solution I, appropriate ammonium metavanadate is dissolved in the water obtains the solution II, get the appropriate zinc nitrate wiring solution-forming III that is dissolved in the water, solution I II III is mixed to get the solution IV, the solution IV is placed in boiling water bath to be heated, add simultaneously appropriate Ludox and KOH solution to mix making beating, then the pH value with ammoniacal liquor adjusting slurry is 5, obtain required catalyst pulp (solid content 15%) after fully stirring, 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 6h, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst A, it is made and consists of:
85％Fe
100V
5.0Zn
20K
0.1O
x+15％SiO
2
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 2]
Getting a certain amount of ferric nitrate is dissolved in the water and is made into certain density solution I, appropriate niobium hydroxide is dissolved in obtains the solution II in oxalic acid solution, get appropriate zinc nitrate, copper nitrate wiring solution-forming III soluble in water, solution I II III is mixed to get the solution IV, the solution IV is placed in boiling water bath heats, add simultaneously appropriate Ludox and Na
2CO
3Solution mixes making beating, then the pH value with ammoniacal liquor adjusting slurry is 1, obtain required catalyst pulp (solid content 45%) after fully stirring, with this slurry spray drying forming, the spraying machine inlet temperature is 200 ℃, 100 ℃ of outlet temperatures, then carry out roasting, 600 ℃ of sintering temperatures, roasting time 0.15h, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst B, it is made and consists of:
20％Fe
100Nb
60.0Zn
5.0Cu
3.0Na
10.0O
x+80％SiO
2
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 3]
getting a certain amount of ferric nitrate is dissolved in the water and is made into certain density solution I, the appropriate ammonium metavanadate that is dissolved in the water and the appropriate niobium hydroxide that is dissolved in oxalic acid solution are mixed to get the solution II, solution I II is mixed to get the solution III, the solution III is placed in boiling water bath to be heated, add simultaneously appropriate aluminium colloidal sol and LiOH solution to mix making beating, then the pH value with ammoniacal liquor adjusting slurry is 3, obtain required catalyst pulp (solid content 35%) after fully stirring, with this slurry spray drying forming, the spraying machine inlet temperature is 230 ℃, 140 ℃ of outlet temperatures, then carry out roasting, 400 ℃ of sintering temperatures, roasting time 4h, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst C, it is made and consists of:
50％Fe
100V
15.0Nb
15.0Li
7.0O
x+50％Al
2O
3
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 4]
getting a certain amount of ferric nitrate is dissolved in the water and is made into certain density solution I, appropriate ammonium metavanadate is dissolved in the water obtains the solution II, get appropriate copper nitrate, the magnesium nitrate wiring solution-forming III that is dissolved in the water, solution I II III is mixed to get the solution IV, the solution IV is placed in boiling water bath to be heated, add simultaneously appropriate Ludox and RbOH solution to mix making beating, then the pH value with ammoniacal liquor adjusting slurry is 2.5, obtain required catalyst pulp (solid content 30%) after fully stirring, with this slurry spray drying forming, the spraying machine inlet temperature is 280 ℃, 150 ℃ of outlet temperatures, then carry out roasting, 550 ℃ of sintering temperatures, roasting time 2h, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst D, it is made and consists of:
40％Fe
100V
23.0Cu
10.0Mg
3.4K
4.5O
x+60％SiO
2
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 5]
getting a certain amount of ferric nitrate is dissolved in the water and is made into certain density solution I, appropriate niobium hydroxide is dissolved in obtains the solution II in oxalic acid solution, get the appropriate zinc nitrate wiring solution-forming III that is dissolved in the water, solution I II III is mixed to get the solution IV, the solution IV is placed in boiling water bath to be heated, add simultaneously appropriate aluminium colloidal sol and CsOH solution to mix making beating, then the pH value with ammoniacal liquor adjusting slurry is 3.7, obtain required catalyst pulp (solid content 25%) after fully stirring, with this slurry spray drying forming, the spraying machine inlet temperature is 320 ℃, 160 ℃ of outlet temperatures, then carry out roasting, 450 ℃ of sintering temperatures, roasting time 1h, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst E, it is made and consists of:
65％Fe
100Nb
45.0Zn
11.5Cs
8.1O
x+35％Al
2O
3
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 6]
Getting a certain amount of ferric nitrate is dissolved in the water and is made into certain density solution I, appropriate ammonium metavanadate is dissolved in the water obtains the solution II, get the appropriate zinc nitrate wiring solution-forming III that is dissolved in the water, solution I II III is mixed to get the solution IV, the solution IV is placed in boiling water bath heats, add simultaneously appropriate aluminium colloidal sol and K
2CO
3Solution mixes making beating, then the pH value with ammoniacal liquor adjusting slurry is 3.1, obtain required catalyst pulp (solid content 20%) after fully stirring, with this slurry spray drying forming, the spraying machine inlet temperature is 250 ℃, 135 ℃ of outlet temperatures, then carry out roasting, 650 ℃ of sintering temperatures, roasting time 3.5h, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst F, it is made and consists of:
60％Fe
100V
25.0Zn
5.5K
4.5O
x+40％Al
2O
3
Prepared catalyst carries out the experimental result of Fischer-Tropsch synthesis and lists 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 90%Fe
100V
5.0Zn
20K
0.1O
x+ 10%SiO
2
Comparative example 2 15%Fe
100V
25.0Zn
5.5K
4.5O
x+ 20%Al
2O
3
Comparative example 3 60%Fe
100V
2.5Zn
20K
4.5O
x+ 40%Al
2O
3
Comparative example 4 40%Fe
100V
23.0Cu
20.0Mg
3.4K
4.5O
x+ 60%SiO
2
Prepared catalyst carries out Fischer-Tropsch synthesis under following reaction condition, result is also listed in table 1.
The reducing condition of above-described embodiment and comparative example is:
450 ℃ of temperature
Pressure 0.5MPa
Loaded catalyst 100 grams
Catalyst loading 2500 hours
-1
Reducing gases H
2/ CO=2/1
36 hours recovery times
Reaction condition is:
300 ℃ of reaction temperatures
Reaction pressure 1.5MPa
Loaded catalyst 100 grams
Catalyst loading 3000 hours
-1
The raw material proportioning (mole) H
2/ CO=2/1
The evaluation result of table 1 embodiment catalyst
Claims (3)
1. the ferrum-based catalyst of the synthetic light hydrocarbon of a Fischer-Tropsch, this catalyst is take the oxide of Si or Al as carrier, and active component contains with atomic ratio measuring, the composition that chemical formula is following:
Fe100A
aB
bC
cO
x
In formula, A is selected from least a in V or Nb;
B is selected from least a in Cu or Zn;
C is selected from least a in alkali metal;
The span of a is 5.0～60.0;
The span of b is 0～20.0;
The span of c is 0.1～10.0;
X satisfies the required oxygen atom sum of each element valence in catalyst;
The carrier consumption is 15～80% of catalyst weight by weight percentage.
2. Fischer-Tropsch claimed in claim 1 synthesizes the preparation method of the ferrum-based catalyst of light hydrocarbon, comprises following processing step:
(1) with the aequum soluble ferric iron salt solution I of making soluble in water;
(2) in the aequum ammonium metavanadate is soluble in water or oxalic acid solution that the aequum niobium hydroxide is dissolved in or two solution are mixed and made into solution II by a certain percentage;
(3) with the aequum solubility category-B salt solution III of making soluble in water;
(4) solution I solution, II solution, III solution mixing system are become mixed solution I V;
(5) in boiling water bath with aequum SiO
2Or Al
2O
3Colloidal sol and hydroxide or the salting liquid of C class join in solution IV, mix making beating, the pH value that adds simultaneously acid-base modifier to regulate slurry is 1～5 to obtain slurry V, solid content is 15～45wt%;
(6) send into the spray dryer spray shaping after slurry V is cooled to 20～60 ℃, then 400～750 ℃ of roasting temperatures 0.15～6 hour, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst.
3. prepare according to claim 2 fluid bed with the preparation method of iron-base fischer-tropsch synthesis catalyst, it is characterized in that sintering temperature is preferably 450～700 ℃, roasting time is preferably 0.5～5 hour.
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| EP3023147A4 (en) * | 2013-07-18 | 2017-07-05 | China University of Petroleum-Beijing | Iron-based hydrogenation catalyst and applications thereof |
Families Citing this family (8)
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| CN103736499B (en) * | 2012-10-17 | 2016-06-08 | 中国石油化工股份有限公司 | Fluid bed synthesis gas alkene ferrum-based catalyst processed, preparation method and its usage |
| CN103962148B (en) * | 2013-01-29 | 2016-05-18 | 中国石油化工股份有限公司 | Directly prepare fluid catalyst and the production method thereof of low-carbon alkene for the synthesis of gas |
| CN104107699B (en) * | 2013-04-16 | 2016-06-08 | 中国石油化工股份有限公司 | Ferrum-based catalyst for synthesizing low-carbon alkene and preparation method thereof |
| CN104437532B (en) * | 2013-09-24 | 2017-03-15 | 中国石油化工股份有限公司 | Fixed bed producing light olefins catalyst, preparation method and its usage |
| CN105363458B (en) * | 2014-08-27 | 2017-12-15 | 中国石油化工股份有限公司 | Synthesize catalyst of light hydrocarbon and preparation method thereof |
| CN105435803B (en) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | Catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof |
| CN105363463B (en) * | 2014-08-27 | 2017-12-15 | 中国石油化工股份有限公司 | Catalyst of synthesis gas light hydrocarbon and preparation method thereof |
| CN105363464B (en) * | 2014-08-27 | 2018-01-09 | 中国石油化工股份有限公司 | Catalyst of synthesis gas light hydrocarbon directly processed and preparation method thereof |
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| WO2003043734A1 (en) * | 2001-11-22 | 2003-05-30 | Sasol Technology (Proprietary) Limited | Ferrihydrite and aluminium-containing fischer-tropsch catalysts |
| CN1562471A (en) * | 2004-03-29 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Iron base catalyzer through Fischer-Tropsch synthesis and preparation method |
| CN101293206A (en) * | 2008-04-21 | 2008-10-29 | 神华集团有限责任公司 | Iron base catalyst for fischer-tropsch synthesis and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003043734A1 (en) * | 2001-11-22 | 2003-05-30 | Sasol Technology (Proprietary) Limited | Ferrihydrite and aluminium-containing fischer-tropsch catalysts |
| CN1562471A (en) * | 2004-03-29 | 2005-01-12 | 中国科学院山西煤炭化学研究所 | Iron base catalyzer through Fischer-Tropsch synthesis and preparation method |
| CN101293206A (en) * | 2008-04-21 | 2008-10-29 | 神华集团有限责任公司 | Iron base catalyst for fischer-tropsch synthesis and preparation method thereof |
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| EP3023147A4 (en) * | 2013-07-18 | 2017-07-05 | China University of Petroleum-Beijing | Iron-based hydrogenation catalyst and applications thereof |
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