CN106607053B - Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof - Google Patents
Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the Fe-Mn catalyst and preparation method thereof that a kind of synthesis gas for fluidized bed directly prepares low-carbon alkene, it mainly solves in the prior art since Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, cooling is difficult in reactor, easy temperature runaway, the problem for making catalyst be easy to inactivate and low-carbon alkene weight selectivities are low.Based on parts by weight, including following components: a) 10~70 parts of carriers, carrier are at least one of the oxide selected from Si or Al to the catalyst that the present invention uses；B) 30~90 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula: Fe100MnaBbCcOx, B is selected from one of Pd or Pt；C is selected from one of alkaline-earth metal；It preferably solves the above problem, the industrial production of low-carbon alkene is directly prepared for synthesis gas.
Description
Technical field
The present invention relates to a kind of Fe-Mn series catalysts and preparation method thereof that low-carbon alkene is directly prepared for synthesis gas
Background technique
Using synthesis gas, (main component is CO and H2) under the effect of the catalyst synthesize hydrocarbon Fischer-Tropsch (Fascher-
Tropsch) synthesis process is an important channel of coal and natural gas indirect liquefaction.This method is nineteen twenty-three by German science
Family's Frans Fischer and Hans Tropsch invention, i.e. heterogeneous catalysis hydrogenation occurs on metallic catalyst for CO,
Generate the process of the mixture based on linear paraffin and alkene.
Germany has just carried out research and development in the twenties in last century, and realizes industrialization in 1936, after World War II because
It can not economically compete and close with petroleum industry；South Africa possesses coal resources abundant, but petroleum resources plaque is weary, and long-term
It is limited by international community's economy and political sanction, forces it to develop coal-to-oil industry technology, and built up first in 1955
Seat production capacity is 25~400,000 tons of product/year coal base F-T synthetic oil factories (Sasol-1).
1973 and 1979 world oil crisis twice cause world's crude oil price to fall and swing fluctuating, big rise and big fall,
It is laid in based on the considerations of Strategic Technology, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, south
Non- Sasol company builds up in succession again and Liang Zuomeiji synthetic oil factory of having gone into operation.But World oil price in 1986 plummets, and postpones
Heavy industrialization process of the F-T synthetic technology in other countries.Since twentieth century nineties, petroleum resources are increasingly short
And in poor quality, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies attract extensive attention again, and Fischer-Tropsch is closed
Significant progress has also been obtained at technology.
The characteristics of China's energy is that rich coal lacks gas oil starvation, and environmental pollution caused by coal directly burns is also increasingly by weight
Depending on not only can reduce on the energy to foreign countries so exploitation is converted into the process of oil product by coal/natural gas through synthesis gas
Dependence, and for solve it is coal-fired caused by problem of environmental pollution have great importance.
Currently used fischer-tropsch catalysts, from active component for be divided into two major classes: ferrum-based catalyst and cobalt-based catalyst
Agent；And common synthesis technology is divided into two major classes if classifying from synthesis condition angle: high temperature fischer-tropsch synthesis technology and low temperature
Fischer-tropsch synthesis process；Synthesis technology is divided into three categories if classifying from used reactor difference: fixed bed F- T synthesis
Technique, fluidized bed fischer-tropsch synthesis process (have the recirculating fluidized bed of early stage and developed on the basis of recirculating fluidized bed later
It is fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technology.Fixed bed therein and slurry bed system are generally used for Low Temperature Fischer Tropsch work
Skill is chiefly used in the production of mink cell focus and wax, and fluidized bed is then more suitable for the high temperature fischer-tropsch work of the production more hydro carbons of lightweight
Skill
It is to be suitable for cryogenic high pressure paste state bed reactor that the fischer-tropsch catalysts of document and patent report are more in recent years
Produce high-carbon long chain hydrocarbons, it is general it is mostly is precipitated iron catalyst or immersion-type Co catalysts.If Rentech company, the U.S. is special
A kind of F- T synthesis precipitated iron catalysis suitable for paste state bed reactor is just reported in sharp USP5504118 and CN1113905A
The preparation method of agent.The characteristics of F- T synthesis of light hydrocarbon is general mostly to carry out in a fluidized bed reactor, the technique is reaction temperature
Degree is higher, and conversion ratio is higher, and there is no the difficulties of solid-liquor separation.Currently reported is applied to the more of fluidized bed F- T synthesis
For molten iron type catalyst, occasionally there is some type of precipitated iron catalyst.One kind is referred to if in patent CN1704161A to be used for
The preparation of the molten iron type catalyst of F- T synthesis is referred to a kind of precipitated iron for fluidized bed in patent CN1695804A and is catalyzed
Agent.
Preparing low-carbon olefin has direct method and indirect method, is specific under so-called direct method i.e. specified conditions
High temperature fischer-tropsch synthesis under catalyst.Although at present have it is some by fixed bed applications in high temperature fischer-tropsch be used for low-carbon alkene production
It attempts, such as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but since Fischer-Tropsch synthesis is strong exothermal reaction, uses fixed bed
When, cooling is difficult in reactor, Yi Feiwen, and catalyst is made to be easy inactivation, these trials terminate in laboratory stage.Fluidized bed can
To overcome these problems existing for fixed bed well, but prepared by the catalyst or the precipitation method that are either prepared using molten iron method
Fluidized Multicomponent Metallic Oxides Catalysts wide, the low disadvantage of selectivity of light olefin that all there is product distribution at present.
Summary of the invention
The first technical problem to be solved by the present invention is existing in the prior art since Fischer-Tropsch synthesis is to put by force
Thermal response, when using fixed bed, reaction cooling is difficult, Yi Feiwen, and catalyst is made to be easy inactivation and the selection of low-carbon alkene weight
Property low problem, a kind of Fe-series catalyst of new direct synthesizing low-carbon alkene of synthesis gas is provided.The catalyst is used for synthesis gas
When direct synthesizing low-carbon alkene, have reaction cooling fast, is not easy temperature runaway and the high advantage of low-carbon alkene weight selectivities.
The technical solution adopted by the present invention one is as follows to solve above-mentioned technical problem: a kind of synthesis gas directly prepares low-carbon alkene
The Fe-Mn catalyst of hydrocarbon.Based on parts by weight, including following components: a) 10~70 parts of carriers, carrier are selected from Si to the catalyst
Or at least one of oxide of Al；B) 30~90 parts of active components, active component contain with atomic ratio measuring chemical formula such as
Fe100MnaBbCcOxComposition, wherein B is selected from least one of Pt or Pd, and C is selected from least one of alkaline-earth metal, a
Value range be 2.5~250.0, b value range be 0.1~10.0, c value range be 0.5~20.0, x be meet
The sum of oxygen atom needed for each element chemical valence in catalyst.
It also includes element D that catalyst formulation, which is preferably active component, in above-mentioned technical proposal, and D is at least the one of Cl or Br
Kind, the ratio of D and Fe are Fe:D=100:d with atomic ratio measuring, and the value range of d is 0.01~2.
Carrier dosage preferred scope is 15~65%, a of catalyst weight by weight percentage in above-mentioned technical proposal
Value preferred scope be 5~200.0, b value preferred scope be 0.5~8.0, c value preferred scope be 1.0~
18.0, d value preferred scope is 0.03~1.75.
The technical solution adopted by the present invention two is as follows to solve above-mentioned technical problem: synthesis gas directly prepares low-carbon alkene
The preparation method of Fe-Mn catalyst, comprises the following steps that:
(1) by Dissolvable Fe salt with B salt is soluble in water that solution is made；Then be obtained by filtration after alkaline precipitating agent cocurrent it is mixed
Close sediment I；
(2) solution II is made by Mn salt is soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) SiO will be selected from2Or Al2O3At least one of colloidal sol and C class hydroxide or salting liquid and D change
Polymer solution is added in slurry III, is mixed with beating, while the pH value that acid-base modifier adjusting slurry is added is starched for 1~5
Material IV, the solid content of slurry IV are 15~45 weight %；
(5) slurry IV is sent into spray dryer spray shaping, it is then small in 400~750 DEG C of roasting temperatures 0.15~6
When, obtain microspheroidal Fe-Mn series catalysts.
The range of inlet temperature is 200~380 DEG C in the spray shaping condition of catalyst described in above-mentioned technical proposal, out
The range of mouth temperature is 100~230 DEG C.
The preferred scope of catalyst maturing temperature described in above-mentioned technical proposal is 450~700 DEG C, the catalyst roasting
The preferred scope of time is 0.5~5h.
Catalyst is can be improved into due to the addition of precious metals pt or Pd in the catalyst according to said method obtained plus hydrogen
Can so that the conversion ratio of catalyst improves, but the effect of Mn can then inhibit alkene further add hydrogen so that product
The amount of middle alkene is far longer than the amount of alkane, and the poisoning of slight Cl or Br can then cooperate with to press down with precious metals pt or Pd
The excessive carbonization of catalyst surface processed allows catalyst to guarantee the long-play under high activity, special preparation method
So that the duct of preformed catalyst is more conducive to formation and the desorption of lower carbon number hydrocarbons, while making the active component of catalyst as far as possible
Dispersion reduces active component because reuniting caused by area carbon, allow the catalyst keep for a long time high conversion ratio with
And the selectivity of high low-carbon alkene, it is highly suitable for the industrial application of the direct synthesizing low-carbon alkene of synthesis gas.
Above-mentioned catalyst is reacted for F- T synthesis low-carbon alkene, using synthesis gas as unstripped gas, H2It is 3 with CO molar ratio,
It is 1.5MPa in reaction pressure, reaction temperature is 350 DEG C, and reaction volume air speed is 10000 hours-1Under conditions of, in fluidized bed
Unstripped gas is contacted with catalyst in reactor, and achieve preferable technical effect: the conversion ratio of CO is up to 97%, Dan Shi C2 =-C4 =
The weight selectivities of (ethylene, propylene and butylene) component are up to 73%.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
The Fe(NO3)39H2O of 606.03g and the five water platinum tetrachloride wiring solution-formings soluble in water of 16.0g are taken, then this is molten
Be centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times it is fresh without miscellaneous
The mixed precipitation I of the iron hydroxide and platinum oxide of matter；Add a certain amount of water that solution is made the manganese nitrate of 50 weight % of 13.45g
II, solution II is mixed into peptization with mixed sediment I and obtains colloidal slurry III；The SiO for being 40% by 49.5g weight content2
The magnesium nitrate hexahydrate of colloidal sol and 76.92g are added in slurry III, are mixed with beating, and dilute salt of 0.11g5 weight % is then added
Acid is 5 with the pH value that ammonium hydroxide adjusts slurry, obtains sol form and be uniformly dispersed and place the uniform sizing material IV that will not be layered for a long time
(solid content 45%), by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, then into
Row roasting, obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese with synthesis gas by 750 DEG C of maturing temperature, calcining time 6h
Series catalysts, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
90 weight %Fe100Mn2.5Pt0.1Mg20.0Cl0.01Ox+ 10 weight %SiO2。
[embodiment 2]
The palladium chloride of the Fe(NO3)39H2O and 26.60g that take 606.03g wiring solution-forming soluble in water, the then solution
It is centrifugated with after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh free from admixture afterwards three times
The mixed precipitation I of iron hydroxide and palladium oxide；The manganese nitrate of 1345g50% is dissolved in the water, solution II is made, by solution II
Peptization, which is mixed, with mixed sediment I obtains colloidal slurry III；The Al for being 25% by 1016g weight content2O3Colloidal sol and 35.42g
Calcium nitrate tetrahydrate is added in slurry III, is mixed with beating, and 5 weight % dilute hydrobromic acid of 48.6g is then added, adjusts slurry
PH value is 1, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 15%) that will not be layered for a long time, by the slurry
Expect spray drying forming, spraying machine inlet temperature is 200 DEG C, 100 DEG C of outlet temperature, is then roasted, maturing temperature 450
DEG C, calcining time 0.15h obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, is made
Group becomes (except special identifier all components ratio is atomic ratio):
60 weight %Fe100Mn250.0Pd10.0Ca10.0Br2.0Ox+ 40 weight %Al2O3。
[embodiment 3]
Take 367.43g ironic citrate and the five water platinum tetrachloride wiring solution-formings soluble in water of 160g, then the solution with
It is centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, the hydrogen for obtaining fresh free from admixture afterwards three times is washed with deionized
The mixed precipitation I of iron oxide and platinum oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 26.90g, it will
Solution I and mixed sediment II are mixed with beating to obtain colloidal slurry III；By the SiO of 435g weight content 40%2Colloidal sol with
63.49g strontium nitrate is added in slurry III, is mixed with beating, and the dilute hydrochloric acid of 0.33g5 weight % is then added, adjusts the pH of slurry
Value is 3, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 35%) that will not be layered for a long time, by the slurry
Spray drying forming, spraying machine inlet temperature are 230 DEG C, 140 DEG C of outlet temperature, are then roasted, 400 DEG C of maturing temperature,
Calcining time 5h obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, and group, which is made, to be become
(except special identifier all components ratio is atomic ratio):
50 weight %Fe100Mn5.0Pt1.0Sr20.0Cl0.03Ox+ 50 weight %SiO2
[embodiment 4]
The palladium chloride of the Fe(NO3)39H2O and 0.53g that take 606.03g wiring solution-forming soluble in water, then the solution with
It is centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, the hydrogen for obtaining fresh free from admixture afterwards three times is washed with deionized
The mixed precipitation I of iron oxide and palladium oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 1076g, it will be molten
Liquid I and mixed sediment II are mixed with beating to obtain colloidal slurry III；The SiO for being 40% by 1150g weight content2Colloidal sol and
The TiO that 1380g weight content is 20%2Colloidal sol and 3.92g barium nitrate are added in slurry III, are mixed with beating, are then added
The dilute hydrochloric acid of 19.25g5 weight %, while the pH value for adjusting slurry is 2.5, obtains sol form and is uniformly dispersed and places for a long time
The uniform sizing material IV (solid content 30%) that will not be layered, by the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C,
It 150 DEG C of outlet temperature, is then roasted, 700 DEG C of maturing temperature, calcining time 0.5h, the conjunction of microspheroidal fluidized bed must be obtained
Low-carbon alkene iron-manganese series catalyzer is directly prepared at gas, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
30 weight %Fe100Mn200.0Pd0.5Ba1.0Cl1.75Ox+ 30 weight %Al2O3+ 40 weight %SiO2
[embodiment 5]
The palladium chloride of the Fe(NO3)39H2O and 21.28g that take 606.03g wiring solution-forming soluble in water, the then solution
It is centrifugated with after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh free from admixture afterwards three times
The mixed precipitation I of iron hydroxide and palladium oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 26.90g,
It is mixed with beating solution I and mixed sediment II to obtain colloidal slurry III；By the SiO of 435g weight content 40%2Colloidal sol with
The magnesium nitrate hexahydrate of 53.13g calcium nitrate tetrahydrate and 19.23g are added in slurry III, are mixed with beating, are then added
The dilute hydrochloric acid of 0.33g5 weight % is 3.5 with the pH value that weak aqua ammonia adjusts slurry, obtains sol form and is uniformly dispersed and puts for a long time
The uniform sizing material IV (solid content 25%) that will not be layered is set, by the slurry spray drying forming, spraying machine inlet temperature is 330
DEG C, it 200 DEG C of outlet temperature, is then roasted, 450 DEG C of maturing temperature, calcining time 3.4h, obtains microspheroidal fluidized bed use
Synthesis gas directly prepares low-carbon alkene iron-manganese series catalyzer, and group, which is made, to be become (except special identifier all components ratio is atom
Than):
50 weight %Fe100Mn5Pd8.0Ca15.0Mg5.0Cl0.03Ox+ 50 weight %SiO2
[embodiment 6]
The palladium chloride of the Fe(NO3)39H2O and 0.53g that take 606.03g is dissolved in water wiring solution-forming, then the solution with
It is centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, the hydrogen for obtaining fresh free from admixture afterwards three times is washed with deionized
The mixed precipitation I of iron oxide and palladium oxide；The manganese nitrate of 53.8g50 weight % is dissolved in the water, solution II is made, by solution
II is mixed with beating to obtain colloidal slurry III with mixed sediment I；By the Al of 800g weight content 25%2O3Colloidal sol and 19.23g
Magnesium nitrate hexahydrate be added in slurry III, be mixed with beating, then be added 19.25g5 weight % dilute hydrochloric acid, adjust slurry
PH value be 4.5, obtain sol form and be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time, general
The slurry spray drying forming, spraying machine inlet temperature are 360 DEG C, 220 DEG C of outlet temperature, are then roasted, maturing temperature
It 550 DEG C, calcining time 1.4h, obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, make
Become in groups (except special identifier all components ratio is atomic ratio):
45 weight %Fe100Mn10.0Pd0.2Mg5.0Cl1.75Ox+ 55 weight %Al2O3。
[embodiment 7]
Take the palladium chloride wiring solution-forming soluble in water of the Fe(NO3)39H2O 13.3g of 606.03g, then the solution with
It is centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, the hydrogen for obtaining fresh free from admixture afterwards three times is washed with deionized
The mixed precipitation I of iron oxide and palladium oxide；The manganese nitrate of 53.8g50 weight % is dissolved in the water, solution II is made, by solution
II is mixed with beating to obtain colloidal slurry III with mixed sediment I；By the SiO of 41.35g weight content 40%2Colloidal sol and
33.08g weight content 25%Al2O3It is added in slurry III, is mixed with beating with the magnesium nitrate hexahydrate of 76.92g, be then added
The 5 weight % dilute hydrobromic acid of dilute hydrochloric acid and 0.73g of 0.33g5 weight %, the pH value for adjusting slurry is 3.5, obtains sol form point
The uniform sizing material IV (solid content 25%) that will not be layered is dissipated uniformly and places for a long time, it is spraying by the slurry spray drying forming
Machine inlet temperature is 260 DEG C, 130 DEG C of outlet temperature, is then roasted, 550 DEG C of maturing temperature, calcining time 4h is obtained micro-
Spherical fluidized bed directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, and group, which is made, to be become (except all groups of special identifier
Divide than being atomic ratio):
85 weight %Fe100Mn10.0Pd5.0Mg20.0Cl0.03Br0.03Ox+ 10 weight %SiO2+ 5 weight %Al2O3
[embodiment 8]
The Fe(NO3)39H2O of 606.03g and the five water platinum tetrachloride wiring solution-formings soluble in water of 80.0g are taken, then this is molten
It is centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh free from admixture afterwards three times
Iron hydroxide and platinum oxide mixed precipitation I；The manganese nitrate of 53.8g50 weight % is dissolved in the water, solution II is made, it will
Solution II and mixed sediment I are mixed with beating to obtain colloidal slurry III；By the Al of 800g weight content 25%2O3Colloidal sol with
The magnesium nitrate hexahydrate of 76.92g and the potassium hydroxide of 1.68g are added in slurry III, are mixed with beating, are then added
The dilute hydrochloric acid of 19.25g5 weight %, adjust slurry pH value be 1.5, obtain sol form be uniformly dispersed and for a long time place will not
The uniform sizing material IV (solid content 20%) of layering, by the slurry spray drying forming, spraying machine inlet temperature is 290 DEG C, outlet
It 180 DEG C of temperature, is then roasted, 650 DEG C of maturing temperature, it is direct to obtain microspheroidal fluidized bed synthesis gas by calcining time 3h
Low-carbon alkene iron-manganese series catalyzer is prepared, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
45 weight %Fe100Mn10.0Pt0.5Mg20.0K2.0Cl1.75Ox+ 55 weight %Al2O3。
[embodiment 9]
The palladium chloride of the Fe(NO3)39H2O of 606.03g and the five water platinum tetrachlorides of 80.0g and 1.33g is taken to be dissolved in water
Then middle wiring solution-forming is centrifugated after the solution and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized three times
The mixed precipitation I of the iron hydroxide and platinum oxide and palladium oxide of fresh free from admixture is obtained afterwards；By the manganese nitrate of 269g 50%
It is dissolved in the water and solution II is made, be mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；By 440g weight
The SiO that content is 40%2The magnesium nitrate hexahydrate of colloidal sol and 53.13g calcium nitrate tetrahydrate and 19.23g is added in slurry III,
It is mixed with beating, the dilute hydrochloric acid of 19.25g5 weight % is then added, the pH value for adjusting slurry is 4.7, obtains sol form and is uniformly dispersed
And the uniform sizing material IV (solid content 20%) that will not be layered is placed for a long time, by the slurry spray drying forming, spraying machine import
Temperature is 350 DEG C, 215 DEG C of outlet temperature, is then roasted, 650 DEG C of maturing temperature, calcining time 5.2h obtains microspheroidal
Fluidized bed directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, and group, which is made, to be become (except special identifier all components ratio
For atomic ratio):
50 weight %Fe100Mn50Pt0.5Pd0.5Ca15.0Mg5.0Cl1.75Ox+ 50 weight %SiO2
[embodiment 10]
The palladium chloride of the Fe(NO3)39H2O of 606.03g and the five water platinum tetrachlorides of 80.0g and 1.33g is taken to be dissolved in water
Then middle wiring solution-forming is centrifugated after the solution and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized three times
The mixed precipitation I of the iron hydroxide and platinum oxide and palladium oxide of fresh free from admixture is obtained afterwards；By the manganese nitrate of 269g 50%
It is dissolved in the water and solution II is made, be mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；By 440g weight
The SiO that content is 40%2The magnesium nitrate hexahydrate of colloidal sol and 19.23g are added in slurry III, are mixed with beating, are then added
The dilute hydrochloric acid of 19.25g5 weight %, the pH value for adjusting slurry is 5, obtains sol form and is uniformly dispersed and places for a long time and will not divide
The uniform sizing material IV (solid content 45%) of layer, by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, outlet temperature
230 DEG C of degree, is then roasted, 750 DEG C of maturing temperature, calcining time 6h obtains microspheroidal fluidized bed and synthesized with iron-base fischer-tropsch
Catalyst, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
50 weight %Fe100Mn50Pt0.5Pd0.5Mg5.0Cl1.75Ox+ 50 weight %SiO2
[comparative example 1]
The Fe(NO3)39H2O of 606.03g and the five water platinum tetrachloride wiring solution-formings soluble in water of 16.0g are taken, then this is molten
Be centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times it is fresh without miscellaneous
The mixed precipitation I of the iron hydroxide and platinum oxide of matter；Add a certain amount of water that solution is made the manganese nitrate of 50 weight % of 13.45g
II, solution II is mixed into peptization with mixed sediment I and obtains colloidal slurry III；It is 40% by 8442.3g weight content
SiO2The magnesium nitrate hexahydrate of colloidal sol and 19.23g are added in slurry III, are mixed with beating, and are then added 0.11g5 weight %'s
Dilute hydrochloric acid, the pH value for adjusting slurry is 5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV that will not be layered for a long time
(solid content 45%), by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, then into
Row roasting, obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese with synthesis gas by 750 DEG C of maturing temperature, calcining time 6h
Series catalysts, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
5 weight %Fe100Mn2.5Pt0.1Mg20.0Cl0.01Ox+ 95 weight %SiO2。
[comparative example 2]
The Fe(NO3)39H2O of 606.03g and the five water platinum tetrachloride wiring solution-formings soluble in water of 16.0g are taken, then this is molten
Be centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times it is fresh without miscellaneous
The mixed precipitation I of the iron hydroxide and platinum oxide of matter；The SiO for being 40% by 49.5g weight content2Six water of colloidal sol and 76.92g
It closes magnesium nitrate to be added in slurry III, be mixed with beating, the dilute hydrochloric acid of 0.11g5 weight % is then added, the pH value for adjusting slurry is
5, it obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time, which is sprayed
Drying and moulding, spraying machine inlet temperature are 380 DEG C, 230 DEG C of outlet temperature, are then roasted, 750 DEG C of maturing temperature, are roasted
Time 6h obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, is made to organize to become and (remove
Special identifier all components ratio is atomic ratio):
90 weight %Fe100Pt0.1Mg20.0Cl0.01Ox+ 10 weight %SiO2。
[comparative example 3]:
The Fe(NO3)39H2O of 606.03g wiring solution-forming soluble in water is taken, then the solution and 25 weight %'s of 400g is dense
It is centrifugated after ammonium hydroxide cocurrent, the ferric hydroxide precipitate I for obtaining fresh free from admixture afterwards three times is washed with deionized；By 269g
50% manganese nitrate, which is dissolved in the water, is made solution II, is mixed with beating solution II and mixed sediment I to obtain colloidal slurry
Ⅲ；The SiO for being 40% by 440g weight content2Colloidal sol and 53.13g calcium nitrate tetrahydrate are added in slurry III, are mixed with beating,
The pH value for adjusting slurry is 4.7, obtains sol form and is uniformly dispersed and places the IV (solid content of uniform sizing material that will not be layered for a long time
20%), by the slurry spray drying forming, spraying machine inlet temperature is 350 DEG C, 215 DEG C of outlet temperature, is then roasted,
It 650 DEG C of maturing temperature, calcining time 5.2h, obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese systems with synthesis gas urging
Agent, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
50 weight %Fe100Mn50Ca15.0Ox+ 50 weight %SiO2
[comparative example 4]
Fixed bed catalyst is prepared using method described in CN 1395993A, is formulated identical with embodiment 3
Obtained above-mentioned catalyst carries out Fischer-Tropsch synthesis in addition to comparative example 4 under following reaction conditions, as a result
It is listed in table 1.
Reducing condition are as follows:
450 DEG C of temperature
Pressure normal pressure
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 2500 hours-1
Also Primordial Qi H2/ CO=0.25/1
Recovery time 24 hours
Reaction condition are as follows:
38 millimeters of fluidized-bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 10000 hours-1
Raw material proportioning (mole) H2/ CO=3/1
By comparative example 4 by evaluation analysis result is listed in table in fixed bed described in patent CN 1395993A
#It is reacted to data when 2000h
* the data of former patent are selected from.
Claims (9)
1. a kind of Fe-Mn series catalysts for directly preparing low-carbon alkene for synthesis gas, catalyst based on parts by weight, including with
Lower component:
A) 10~70 parts of carriers, carrier are at least one of the oxide selected from Si or Al；
B) 30~90 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula: Fe100MnaBbCcOx
B is selected from least one of Pd or Pt；
C is selected from least one of alkaline-earth metal；
The value range of a is 2.5~250.0；
The value range of b is 0.1~10.0；
The value range of c is 0.5~20.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；
Its active component also includes element D, and D is at least one of Cl or Br, and the ratio of D and Fe are Fe:D=with atomic ratio measuring
The value range of 100:d, d are 0.01~2.
2. the Fe-Mn series catalysts according to claim 1 for directly preparing low-carbon alkene for synthesis gas, it is characterised in that
The value range of a is 5~200.0.
3. the Fe-Mn series catalysts according to claim 1 for directly preparing low-carbon alkene for synthesis gas, it is characterised in that
The value range of b is 0.5~8.0.
4. the Fe-Mn series catalysts according to claim 1 for directly preparing low-carbon alkene for synthesis gas, it is characterised in that
The value range of c is 1.0~18.0.
5. the Fe-Mn series catalysts according to claim 1 for directly preparing low-carbon alkene for synthesis gas, it is characterised in that
Carrier dosage be by weight percentage be the 15~65% of catalyst weight.
6. the Fe-Mn series catalysts according to claim 1 for directly preparing low-carbon alkene for synthesis gas, it is characterised in that
The value range of d is 0.03~1.75.
7. a kind of preparation side for the Fe-Mn series catalysts for directly preparing low-carbon alkene for synthesis gas as described in claim 1
Method comprises the following steps that:
(1) by Dissolvable Fe salt with B salt is soluble in water that solution is made；Then be obtained by filtration after alkaline precipitating agent cocurrent mix it is heavy
Starch I；
(2) solution II is made by Mn salt is soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) SiO will be selected from2Or Al2O3At least one of colloidal sol and the hydroxide or salting liquid of C and the compound of D it is molten
Liquid is added in slurry III, is mixed with beating, while the pH value that acid-base modifier adjusting slurry is added obtains slurry IV for 1~5, starches
The solid content of material IV is 15~45 weight %；
(5) by slurry IV be sent into spray dryer spray shaping, then 400~750 DEG C roasting temperature 0.15~6 hour,
Obtain microspheroidal Fe-Mn series catalysts.
8. the preparation method of the Fe-Mn series catalysts according to claim 7 that low-carbon alkene is directly prepared for synthesis gas,
It is characterized in that the spray shaping condition of catalyst is 200~380 DEG C of inlet temperature, 100~230 DEG C of outlet temperature.
9. the preparation method of the Fe-Mn series catalysts according to claim 7 that low-carbon alkene is directly prepared for synthesis gas,
It is characterized in that maturing temperature is 450~700 DEG C, calcining time is 0.5~5 hour.
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