CN106607059B

CN106607059B - The Fe-Mn series catalysts and preparation method thereof of low-carbon alkene are directly prepared for synthesis gas

Info

Publication number: CN106607059B
Application number: CN201510685929.7A
Authority: CN
Inventors: 庞颖聪; 陶跃武; 宋卫林; 李剑锋
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2015-10-21
Filing date: 2015-10-21
Publication date: 2019-09-06
Anticipated expiration: 2035-10-21
Also published as: CN106607059A

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: Fe₁₀₀MnaB_bC_cO_x, B is selected from one of Re or Os；C is selected from the technical solution of one of alkali metal；It preferably solves the above problem, the industrial production of low-carbon alkene is directly prepared for synthesis gas.

Description

Fe-Mn series catalysts and its preparation of low-carbon alkene are directly prepared for synthesis gas Method

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

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 It relies on, and have great importance for solving problem of environmental pollution caused by fire coal.

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 industrialization was realized in 1936, it is closed after World War II because can not economically be competed with petroleum industry；South Africa possesses abundant Coal resources, but petroleum resources plaque is weary, and is limited for a long time by international community's economy and political sanction, its Development of Coal is forced Oils preparation industry technology, and in 1955 built up First production capacity be 25~400,000 tons product/year coal base F-T synthetic oil factory (Sasol-1).1973 and 1979 world oil crisis twice cause world's crude oil price to fall and swing fluctuating, rise greatly greatly It falls, 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 Africa Sasol company builds up in succession again and Liang Zuomeiji synthetic oil factory of having gone into operation.But plummeting for World oil price in 1986, pushes away Late heavy industrialization process of the F-T synthetic technology in other countries.Since twentieth century nineties, petroleum resources are increasingly short Scarce and in poor quality, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies attract extensive attention again, Fischer-Tropsch Synthetic technology has also obtained significant progress.Currently used fischer-tropsch catalysts, from active component for be divided into two major classes: iron Base catalyst and cobalt-base catalyst；And common synthesis technology is divided into two major classes if classifying from synthesis condition angle: high temperature Fischer-tropsch synthesis process and Low Temperature Fischer Tropsch synthesis technology；Synthesis technology is divided into three if classifying from used reactor difference big Class: fixed bed fischer-tropsch synthesis process, fluidized bed fischer-tropsch synthesis process (have the recirculating fluidized bed of early stage and later ciculation fluidized Developed on the basis of bed fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technology.Fixed bed therein and slurry bed system are general Applied to low temperature fischer-tropsch process, it is chiefly used in the production of mink cell focus and wax, and fluidized bed is then more suitable for production more lightweight The high temperature fischer-tropsch technique of hydro carbons

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.

In order to solve the above technical problems, The technical solution adopted by the invention is as follows: it is a kind of directly prepared for synthesis gas it is low The Fe-Mn series catalysts of carbon olefin, catalyst 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；

B) 30~90 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula: Fe₁₀₀Mn_aB_bC_cO_x

B is selected from least one of Re or Os；

C is selected from least one of alkali 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 0.1~10.0；

X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst.

Preferably, the catalyst also active component also includes element D, and D is at least one of S or P, the ratio of D and Fe It is Fe:D=100:d with atomic ratio measuring, 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 0.5~8.0, The value preferred scope of d is 0.03~1.75.

To solve above-mentioned technical problem two The technical solution adopted by the invention is as follows: F- T synthesis light hydrocarbon iron-based catalysis The preparation method of agent, 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 preferred scope of inlet temperature is 200~380 DEG C in the spray shaping condition of the catalyst, outlet temperature Preferred scope is 100~230 DEG C, and the preferred scope of the catalyst maturing temperature is 450~700 DEG C.

The preferred scope of the catalyst calcining time is 0.5~5h.

Catalyst is can be improved into due to the addition of noble metal Re or Os 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 S or P can then cooperate with to inhibit with noble metal Re or Os The excessive carbonization of catalyst surface allows catalyst to guarantee the long-play under high activity, and special preparation method makes The duct for obtaining preformed catalyst is more conducive to formation and the desorption of lower carbon number hydrocarbons, while the active component of catalyst is divided as far as possible Dissipate, reduce active component because reuniting caused by area carbon, allow the catalyst keep for a long time high conversion ratio and The selectivity of high low-carbon alkene 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 rhenium trichloride of the Fe(NO3)39H2O and 0.44g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of rheium oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 13.45g, by solution II with Mixed sediment I mixes peptization and obtains colloidal slurry III；The SiO for being 40% by 49.5g weight content₂Colloidal sol and 0.084g hydrogen Potassium oxide is added in slurry III, is mixed with beating, and the dilute sulfuric acid of 15 weight % of 0.098g is then added, and adjusts slurry with ammonium hydroxide PH value be 5, obtain sol form and be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time, by this Slurry spray drying forming, spraying machine inlet temperature are 380 DEG C, 230 DEG C of outlet temperature, are then roasted, maturing temperature 750 DEG C, calcining time 6h obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, group is made As (except special identifier all components ratio is atomic ratio):

90 weight %Fe₁₀₀Mn_2.5Re_0.1K_0.1S_0.01O_x+ 10 weight %SiO₂。

[embodiment 2]:

The osmium trichloride of the Fe(NO3)39H2O and 44.49g 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 iron hydroxide afterwards three times With the mixed precipitation I of somuum oxide；The manganese nitrate of 1345g50% is dissolved in the water, solution II is made, by solution II with mix it is heavy Starch I mixes peptization and obtains colloidal slurry III；The Al for being 25% by 1016g weight content₂O₃Colloidal sol adds with 20.47g cesium nitrate Enter into slurry III, be mixed with beating, 19.6g15 weight % phosphoric acid,diluted is then added, is 1 with the pH value that dust technology adjusts slurry, It obtains sol form to be uniformly dispersed and place the uniform sizing material IV (solid content 15%) that will not be layered for a long time, which is done by spraying Dry molding, spraying machine inlet temperature are 200 DEG C, 100 DEG C of outlet temperature, are then roasted, 450 DEG C of maturing temperature, when roasting Between 0.15h, obtain microspheroidal fluidized bed and directly prepare low-carbon alkene iron-manganese series catalyzer with synthesis gas, be made group become (remove Special identifier all components ratio is atomic ratio):

60 weight %Fe₁₀₀Mn_250.0Os_10.0Cs_10.0P_2.0O_x+ 40 weight %Al₂O₃。

[embodiment 3]:

The rhenium trichloride of 367.43g ironic citrate and 3.52g wiring solution-forming soluble in water are taken, then the solution and 400g It is centrifugated after the concentrated ammonia liquor cocurrent of 25 weight %, is washed with deionized and obtains fresh iron hydroxide and rheium oxide afterwards three times Mixed precipitation I；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 26.90g, by solution I and mixed precipitation Object II is mixed with beating to obtain colloidal slurry III；By the SiO of 435g weight content 40%₂Colloidal sol is added to 4.8g sodium hydroxide It in slurry III, is mixed with beating, the dilute sulfuric acid of 0.294g15 weight % is then added, be 3 with the pH value that weak aqua ammonia adjusts slurry, obtain It is uniformly dispersed to sol form and places the uniform sizing material IV (solid content 35%) that will not be layered for a long time, which is spray-dried Molding, 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 Mark all components ratio is atomic ratio):

50 weight %Fe₁₀₀Mn₅Re_8.0Na_8.0S_0.03O_x+ 50 weight %SiO₂

[embodiment 4]:

The osmium trichloride of the Fe(NO3)39H2O and 2.23g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of somuum oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 1076g, by solution I and mixes Sediment II is closed to be mixed with beating to obtain colloidal slurry III；The SiO for being 40% by 1150g weight content₂Colloidal sol and 1380g weight The TiO that content is 20%₂Colloidal sol and 0.77g rubidium hydroxide are added in slurry III, are mixed with beating, and 7.35g15 weight is then added Measure % phosphoric acid,diluted, while with weak aqua ammonia adjust slurry pH value be 2.5, obtain sol form be uniformly dispersed and for a long time place will not The uniform sizing material IV (solid content 30%) of layering, by the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, outlet It 150 DEG C of temperature, is then roasted, 700 DEG C of maturing temperature, calcining time 0.5h must obtain microspheroidal fluidized bed synthesis gas Low-carbon alkene iron-manganese series catalyzer directly is prepared, group, which is made, to be become (except special identifier all components ratio is atomic ratio):

30 weight %Fe₁₀₀Mn_200.0Os_0.5Rb_0.5P_1.75O_x+ 30 weight %Al₂O₃+ 40 weight %SiO₂

[embodiment 5]:

The rhenium trichloride of the Fe(NO3)39H2O and 3.52g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of rheium oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 26.90g, by solution I and mixes Sediment II is closed to be mixed with beating to obtain colloidal slurry III；By the SiO of 435g weight content 40%₂Colloidal sol and 4.8g sodium hydroxide It is added in slurry III, is mixed with beating, the phosphoric acid,diluted of 15 weight % of 0.126g is then added, the pH of slurry is adjusted with weak aqua ammonia Value is 3.5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 25%) that will not be layered for a long time, by the slurry Expect spray drying forming, spraying machine inlet temperature is 330 DEG C, 200 DEG C of outlet temperature, is then roasted, maturing temperature 450 DEG C, calcining time 3.4h 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):

50 weight %Fe₁₀₀Mn₅Re_8.0Na_8.0P_0.03O_x+ 50 weight %SiO₂

[embodiment 6]:

The rhenium trichloride of the Fe(NO3)39H2O and 0.88g that take 606.03g is dissolved in water wiring solution-forming, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of rheium oxide；The manganese nitrate of 53.8g50 weight % is dissolved in the water, solution II is made, by solution II with mix Sediment I is mixed with beating to obtain colloidal slurry III；By the Al of 800g weight content 25%₂O₃Colloidal sol adds with 4.3g potassium hydroxide Enter into slurry III, be mixed with beating, the dilute sulfuric acid of 17.15g15 weight % is then added, is with the pH value that weak aqua ammonia adjusts slurry 4.5, it obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 20%) that will not be layered for a long time, by the pulp spraying Mist drying and moulding, spraying machine inlet temperature are 360 DEG C, 220 DEG C of outlet temperature, are then roasted, 550 DEG C of maturing temperature, are roasted Time 1.4h is burnt, microspheroidal fluidized bed is obtained and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, group, which is made, to be become (except special identifier all components ratio is atomic ratio):

45 weight %Fe₁₀₀Mn_10.0Re_0.2K_5.0S_1.75O_x+ 55 weight %Al₂O₃。

[embodiment 7]:

Take the rhenium trichloride wiring solution-forming soluble in water of the Fe(NO3)39H2O 22.0g of 606.03g, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of rheium oxide；The manganese nitrate of 53.8g50 weight % is dissolved in the water, solution II is made, by solution II with mix Sediment I is mixed with beating to obtain colloidal slurry III；By the SiO of 41.35g weight content 40%₂Colloidal sol and 33.08g weight contain Measure 25%Al₂O₃It is added in slurry III, is mixed with beating with 0.13g potassium hydroxide, the dilute of 15 weight % of 0.294g is then added The phosphoric acid,diluted of 15 weight % of sulfuric acid and 0.126g is 3.5 with the pH value that dust technology adjusts slurry, obtains sol form and be uniformly dispersed And the uniform sizing material IV (solid content 25%) that will not be layered is placed for a long time, by the slurry spray drying forming, spraying machine import Temperature is 260 DEG C, 130 DEG C of outlet temperature, is then roasted, 550 DEG C of maturing temperature, calcining time 4h obtains microspheroidal stream Change bed and directly prepare low-carbon alkene iron-manganese series catalyzer with synthesis gas, group, which is made, to be become (except special identifier all components ratio is Atomic ratio):

85 weight %Fe₁₀₀Mn_10.0Re_5.0K_0.5S_0.03P_0.03O_x+ 10 weight %SiO₂+ 5 weight %Al₂O₃

[embodiment 8]:

The osmium trichloride of the Fe(NO3)39H2O and 2.23g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of somuum oxide；The manganese nitrate of 53.8g50 weight % is dissolved in the water, solution II is made, by solution II with mix Sediment I is mixed with beating to obtain colloidal slurry III；By the Al of 800g weight content 25%₂O₃Colloidal sol adds with 4.3g potassium hydroxide Enter into slurry III, be mixed with beating, the dilute sulfuric acid of 15 weight % of 17.15g is then added, the pH value of slurry is adjusted with dust technology It is 1.5, obtains 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, by the slurry Spray drying forming, spraying machine inlet temperature are 290 DEG C, 180 DEG C of outlet temperature, are then roasted, 650 DEG C of maturing temperature, Calcining time 3h 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):

45 weight %Fe₁₀₀Mn_10.0Os_0.5K_5.0S_1.75O_x+ 55 weight %Al₂O₃。

[embodiment 9]:

The rhenium trichloride of the Fe(NO3)39H2O and 2.20g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of somuum oxide；The manganese nitrate of 269g 50% is dissolved in the water, solution II is made, by solution II and mixed precipitation Object I is mixed with beating to obtain colloidal slurry III；The SiO for being 40% by 440g weight content₂Colloidal sol and 0.084g potassium hydroxide and 10.64g cesium nitrate is added in slurry III, is mixed with beating, and the dilute sulfuric acid of 15 weight % of 17.15g is then added, with ammonium hydroxide tune The pH value for saving 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 %Fe₁₀₀Mn₅₀Re_0.5Cs_5.2K_0.1S_1.75O_x+ 50 weight %SiO₂

[embodiment 10]

Take the osmium trichloride of the Fe(NO3)39H2O of 606.03g and the rhenium trichloride of 2.20g and 23.2g are soluble in water to be made into Then solution is centrifugated after the solution and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains afterwards three times The mixed precipitation I of fresh iron hydroxide and somuum oxide；The manganese nitrate of 269g 50% 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；The SiO for being 40% by 440g weight content₂Colloidal sol with 0.084g potassium hydroxide is added in slurry III, is mixed with beating, and the dilute sulfuric acid of 15 weight % of 17.15g is then added, uses ammonium hydroxide The pH value for adjusting slurry is 5, 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 45%), by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, is then roasted, 750 DEG C of maturing temperature, calcining time 6h obtains microspheroidal fluidized bed iron-base fischer-tropsch synthesis catalyst, is made to organize to become and (remove Special identifier all components ratio is atomic ratio):

50 weight %Fe₁₀₀Mn₅₀Re_0.5Os_5.2K_0.1S_1.75O_x+ 50 weight %SiO₂

[comparative example 1]

The rhenium trichloride of the Fe(NO3)39H2O and 0.44g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of rheium oxide；Add a certain amount of water that solution II is made the manganese nitrate of 50 weight % of 13.45g, by solution II with Mixed sediment I mixes peptization and obtains colloidal slurry III；The SiO for being 40% by 8442.3g weight content₂Colloidal sol and 0.084g Potassium hydroxide is added in slurry III, is mixed with beating, and the dilute sulfuric acid of 15 weight % of 0.098g is then added, and is adjusted and is starched with ammonium hydroxide The pH value of material is 5, 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, will The slurry spray drying forming, spraying machine inlet temperature are 380 DEG C, 230 DEG C of outlet temperature, are then roasted, maturing temperature It 750 DEG C, calcining time 6h, obtains microspheroidal fluidized bed and directly prepares low-carbon alkene iron-manganese series catalyzer with synthesis gas, be made Group becomes (except special identifier all components ratio is atomic ratio):

5 weight %Fe₁₀₀Mn_2.5Re_0.1K_0.1S_0.01O_x+ 95 weight %SiO₂。

[comparative example 2]

The rhenium trichloride of the Fe(NO3)39H2O and 0.44g that take 606.03g wiring solution-forming soluble in water, then the solution with It is centrifugated after the concentrated ammonia liquor cocurrent of 400g25 weight %, is washed with deionized and obtains fresh iron hydroxide and oxygen afterwards three times Change the mixed precipitation I of rhenium；The SiO for being 40% by 49.5g weight content₂Colloidal sol and 0.084g potassium hydroxide are added to mixed precipitation It in I, is mixed with beating, the dilute sulfuric acid of 15 weight % of 0.098g is then added, be 5 with the pH value that ammonium hydroxide adjusts slurry, obtain colloidal sol Shape is uniformly dispersed and places the uniform sizing material II (solid content 45%) that will not be layered for a long time, by the slurry spray drying forming, Spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, is then roasted, 750 DEG C of maturing temperature, calcining time 6h is obtained Low-carbon alkene iron-manganese series catalyzer is directly prepared with synthesis gas to microspheroidal fluidized bed, group, which is made, to be become (except special identifier institute Having component ratio is atomic ratio):

90 weight %Fe₁₀₀Re_0.1K_0.1S_0.01O_x+ 10 weight %SiO₂。

[comparative example 3]:

The rhenium trichloride of the Fe(NO3)39H2O and 2.20g that take 606.03g wiring solution-forming soluble in water, then the solution with Be centrifugated after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, be washed with deionized obtain afterwards three times fresh iron hydroxide and The mixed precipitation I of somuum oxide；The manganese nitrate of 269g 50% is dissolved in the water, solution II is made, by solution II and mixed precipitation Object I is mixed with beating to obtain colloidal slurry III；The SiO for being 40% by 440g weight content₂Colloidal sol and 0.084g potassium hydroxide and 10.64g cesium nitrate is added in slurry III, is mixed with beating, and is 4.7 with the pH value that ammonium hydroxide adjusts slurry, obtains sol form dispersion The uniform sizing material IV (solid content 20%) that will not be layered is placed uniformly and for a long time, by the slurry spray drying forming, spraying machine Inlet temperature is 350 DEG C, 215 DEG C of outlet temperature, is then roasted, 650 DEG C of maturing temperature, calcining time 5.2h 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):

50 weight %Fe₁₀₀Mn₅₀Re_0.5Cs_5.2K_0.1O_x+ 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 3 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 3, by described in patent CN 1395993A, the results are shown in Table 1 for evaluation analysis in fixed bed

The evaluation result of 1 embodiment catalyst of table

^#It is reacted to data when 2000h

* the data of former patent are selected from.

Claims

1. a kind of Fe-Mn series catalysts for directly preparing low-carbon alkene for synthesis gas, catalyst based on parts by weight, by following Component is constituted:

B) 30~90 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula: Fe₁₀₀Mn_aB_bC_cO_xB Selected from least one of Re or Os；

C is selected from least one of alkali 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 0.1~10.0；

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 the ratio of D P, D and Fe are Fe:D=100:d, the value range of d with atomic ratio measuring It is 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 0.5~8.0.

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. the preparation method of the Fe-Mn series catalysts described in claim 1 that low-carbon alkene is directly prepared for synthesis gas, including Following processing step:

(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；

(4) SiO will be selected from₂Or Al₂O₃At least one of colloidal sol and C class hydroxide or salting liquid and D compound Solution 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, The solid content of slurry 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.