CN103933989B - For the synthesis of the Catalysts and its preparation method of low-carbon alkene - Google Patents
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Abstract
The present invention relates to a kind of Catalysts and its preparation method for Fischer-Tropsch synthesizing low-carbon alkene. Mainly solve in prior art because Fischer-Tropsch synthesis is strong exothermal reaction, while using fixed bed, remove heat difficulty in reactor, easily temperature runaway, makes the selective low problem of the easy inactivation of catalyst and low-carbon alkene weight. The catalyst that the present invention adopts, in parts by weight, comprises following component: a) 10～70 parts of carriers, and carrier is at least one being selected from the oxide of Si or Ti; B) 30～90 parts of active components, active component contains with atomic ratio measuring, the composition that chemical formula is following: Fe100AaBbCcOx, A is selected from the one in Ba or Sr; B is selected from the one in Co or Ni; C is selected from a kind of technical scheme in alkali metal, has solved preferably the problems referred to above, can be used for the industrial production of Fischer-Tropsch synthesizing low-carbon alkene.
Description
Technical field
The present invention relates to a kind of ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene 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 petroleum resources and products thereof. China's energyFeature is rich coal weak breath oil starvation, petroleum resources scarcity and the under-supply sternness that has become China's energy development of domestic petroleumReality, along with the development of national economy, contradiction between oil supply and demand will be continuation and expand trend, break away from energy resource structure and provide for oilThe dependence in source has become extremely urgent problem demanding prompt solution. This just impel people actively and hardy go to develop other substituteThe energy, adds the coal environmental pollution that directly burning causes and also increasingly comes into one's own. Exploitation is by the synthetic cyclostrophic of coal/natural gas viaTurn to the process of low-carbon alkene and liquid fuel, not only can reduce on the energy external dependence, and coal-fired for solvingThe problem of environmental pollution causing has great importance.
Fischer-Tropsch (Fascher-Tropsch) is synthetic is to utilize synthesis gas (main component is CO and H2) in the effect of catalystThe process of lower synthetic hydrocarbon is an important channel of coal and natural gas indirect liquefaction. The method is that nineteen twenty-three is by Germany scientistFransFischer and HansTropsch invention, there is heterogeneous catalysis hydrogenation in CO on metallic catalyst, rawBecome the process taking linear paraffin and alkene as main mixture. Germany has just carried out research and development in the twenties in last century, andRealize industrialization in 1936, after World War II because closing with petroleum industry competition economically; South Africa has abundantCoal resources, but petroleum resources plaque is weary, and be subject to for a long time the restriction of international community's economy and political sanction, force its Development of Coal systemOil industrial technology, and built up in 1955 the coal-based F-T artificial oil factory that First production capacity is 25～400,000 tons of product/years(Sasol-1). Twice world oil crisis of 1973 and 1979, cause world's crude oil price to fall to swing fluctuating, large rise largeFall, based on the consideration of Strategic Technology deposit, F-T synthetic technology is aroused the interest of industrialized country again. 1980 and nineteen eighty-two,Two the coal-based artificial oil factories that in succession build up again and gone into operation of South Africa Sasol company. But plummeting of World oil price in 1986, pushes awayF-T synthetic technology is in other national heavy industrialization process late. Since twentieth century nineties, petroleum resources are increasingly shortLack and in poor quality, coal and natural gas proved reserves but constantly increase simultaneously, and fischer-tropsch technologies causes extensive concern, Fischer-Tropsch againSynthetic technology has also obtained significant progress. At present conventional fischer-tropsch catalysts, is divided into two large classes active component: ironCatalyst based and cobalt-base catalyst; And the words that common synthesis technique is classified from synthesis condition angle are divided into two large classes: high temperatureFischer-tropsch synthesis process and low temperature fischer-tropsch synthesis process; It is three large that the words that synthesis technique is classified from used reactor difference are divided intoClass: fixed bed fischer-tropsch synthesis process, fluid bed fischer-tropsch synthesis process (has early stage recirculating fluidized bed and afterwards ciculation fluidizedOut fixed fluidized bed of the upper development in bed basis) and syrup state bed Fischer Tropsch synthesis technique. Fixed bed is wherein general with slurry state bedBe applied to low temperature fischer-tropsch process, be used for the production of mink cell focus and wax, fluid bed is more suitable for produces lightweight comparativelyThe high temperature fischer-tropsch technique of hydro carbons
What the fischer-tropsch catalysts of document and patent report was many in recent years is to be applicable to cryogenic high pressure paste state bed reactorProduce high-carbon long chain hydrocarbon, generally mostly be precipitated iron catalyst, or immersion-type Co catalysts. If Rentech company of the U.S. is speciallyIn profit US5504118 and CN1113905A, just report a kind of synthetic precipitated iron catalyst of Fischer-Tropsch that is applicable to paste state bed reactorPreparation method. Synthetic general how the carrying out in fluidized-bed reactor of Fischer-Tropsch of light hydrocarbon, the feature of this technique is reaction temperatureHigher, conversion ratio is higher, does not have the difficulty of liquid-solid separation. Currently reported be applied to synthetic mostly being of fluid bed Fischer-TropschMolten iron type catalyst, idol has the precipitated iron catalyst of some types. As a kind of for expense in just mentioned in patent CN1704161AHold in the palm the preparation of synthetic molten iron type catalyst, in patent CN1695804A, mentioned a kind of precipitated iron catalysis for fluid bedAgent. But be that the Fluidized Multicomponent Metallic Oxides Catalysts that uses the standby catalyst of molten iron legal system or the precipitation method to prepare all exists product to distributeThe shortcoming wide, selectivity of light olefin is low.
Preparing low-carbon olefin has direct method and indirect method, and so-called direct method is namely specific under specified conditionsHigh temperature fischer-tropsch under catalyst is synthetic. Although having some at present produces in high temperature fischer-tropsch fixed bed applications for low-carbon alkeneAttempt, as German Rule, the DaLian, China Chemistry and Physics Institute, but because Fischer-Tropsch synthesis is strong exothermal reaction, use fixed bedTime, in reactor, remove heat difficulty, easily temperature runaway, makes the easy inactivation of catalyst, and these trials all terminate in laboratory stage, also do not have at presentHave and anyly directly prepare the industrial application in low-carbon alkene aspect about synthesis gas.
Summary of the invention
One of technical problem to be solved by this invention be in prior art, exist because Fischer-Tropsch synthesis is for putting by forceThermal response, while using fixed bed, heat difficulty is removed in reaction, and easily temperature runaway is selected the easy inactivation of catalyst and low-carbon alkene weightProperty low problem, a kind of ferrum-based catalyst of new Fischer-Tropsch synthesizing low-carbon alkene is provided, this catalyst is for Fischer-Tropsch synthesizing low-carbonWhen olefine reaction, there is reaction and remove heat soon, be difficult for the selective high advantage of temperature runaway and low-carbon alkene weight.
The technical solution used in the present invention is as follows: a kind of ferrum-based catalyst of Fischer-Tropsch synthesizing low-carbon alkene, this catalyst withParts by weight meter, comprises following component: a) 10～70 parts of carriers, and carrier is at least one being selected from the oxide of Si or Ti;B) 30～90 parts of active components, active component contains with atomic ratio measuring, the composition that chemical formula is following: Fe100AaBbCcOx, A choosingOne in Ba or Sr, B is selected from the one in Co or Ni, and C is selected from the one in alkali metal, and the span of a is 0.5～The span of 200.0, b is that the span of 0.1～10.0, c is 0.1～10.0.
In technique scheme, the active component of catalyst also includes element D, and D is at least one of P or S, D and Fe'sRatio is taking atomic ratio measuring as Fe:D=100:d, and the span of d is 0.01 ~ 2.0; The preferable range of vector contg is 15～65Part; The value preferable range of a is 0.8～150.0; The value preferable range of b is 0.8～45.0; The value preferable range of c is0.15～9.0; The value preferable range of d is 0.03 ~ 1.75.
As follows for solving the problems of the technologies described above two the technical solution used in the present invention: for the iron of Fischer-Tropsch synthesizing low-carbon alkeneCatalyst based preparation method, comprises following processing step:
(1) by the solution I of making soluble in water soluble ferric iron salt;
(2) by the salt containing A component and the salt solution of making soluble in water that contains B component, then (will with alkaline precipitating agent streamSalting liquid and alkaline precipitating agent join in same container simultaneously, and the unit interval enters salting liquid and the alkaline sedimentation of this containerAgent just in time can complete reaction precipitation) filter the mixed oxide II that obtains A and B after precipitation;
(3) solution I is mixed to making beating with mixed oxide II and obtain slurry III;
(4) will be selected from SiO2Or TiO2In at least one colloidal sol and containing hydroxide or the salting liquid and rare of C componentAt least one of phosphoric acid or dilute sulfuric acid joins in slurry III, mixes making beating, adds acid-base modifier to regulate the pH of slurry simultaneouslyValue is 1 ~ 5 to obtain slurry IV, and slurry IV solid content is 15 ~ 45 % by weight;
(5) slurry IV is sent into spray dryer spray shaping, then little at 400 ~ 750 DEG C of roasting temperatures 0.15 ~ 6Time, obtain microsphere shaped iron based catalyst.
The preferred version of method for preparing catalyst is soluble ferric iron salt and the salt system soluble in water that contains D component in step (1)Become solution I; The preferable range that the spray shaping condition of described catalyst is inlet temperature is 200 ~ 380 DEG C, outlet temperature excellentSelecting scope is 100 ~ 230 DEG C; The preferable range of described catalyst sintering temperature is 450 ~ 700 DEG C; Described catalyst roasting timePreferable range be 0.5 ~ 5 hour.
The catalyst according to said method obtaining is due to the hydrogenation activity that can greatly improve catalyst that adds of a small amount of Co or Ni,Ba or Sr can improve the chemisorbed performance of catalyst to CO, and the synergy of the two can improve the work of catalyst greatlyProperty, simultaneously sulfur poisoning a little or phosphorism can suppress the further hydrogenation of alkene, stop the generation of excessive alkane, makeThe amount that obtains alkene in product is far longer than the amount of alkane, the more bonus point of active component of the catalyst of special preparation method's mouldingLoose, active surface can be more, and the duct meanwhile forming is more conducive to formation and the desorption of lower carbon number hydrocarbons, these characteristics and eachCooperative effect between individual component makes this catalyst be very beneficial for the synthetic of low-carbon alkene, and detailed evaluation result is shown in attachedTable.
Above-mentioned catalyst is used for Fischer-Tropsch synthesizing low-carbon olefine reaction, taking synthesis gas as unstripped gas, and H2With CO mol ratio be 2,Be 1.75MPa in reaction pressure, reaction temperature is 300 DEG C, and reaction volume air speed is 10000 hours-1Condition under, at fluid bedReactor Raw gas contacts with catalyst, and the conversion ratio of having obtained good technique effect: CO can reach 93%, C2 =-C4 =(secondAlkene, propylene and butylene) weight of component selectively can reach 70%.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 1.96g barium nitrate and 218.3g six hydrationsCobalt nitrate is dissolved in the water and makes solution, then by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 450g, by this precipitationFilter, and by the mixed oxide II that obtains fresh clean barium monoxide and cobalt oxide after deionized water cyclic washing, by solution IMix making beating with mixed oxide II and obtain slurry III; By the SiO of 49.3g weight content 40%2Colloidal sol and 0.084g potassium hydroxideAnd 0.098g15 % by weight dilute sulfuric acid joins in slurry III, mix making beating, regulate the pH value of slurry with ammoniacal liquor is 5 simultaneously, mustTo slurry IV (solid content 15wt%), by this slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, outlet temperature 230DEG C, then carry out roasting, 750 DEG C of sintering temperatures, roasting time 6h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyticAgent, it is made and consists of (except special identifier all components is than being atomic ratio):
90 % by weight Fe100Ba0.5Co50K0.1S0.01Ox+ 10 % by weight SiO2。
[embodiment 2]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 784g barium nitrate and 2.18g six hydration nitreAcid cobalt is dissolved in the water and makes solution, then, by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 1800g, this is precipitatedFilter, and by the mixed oxide II that obtains fresh clean barium monoxide and cobalt oxide after deionized water cyclic washing, by solution I andMixed oxide II is mixed making beating and is obtained slurry III; By the SiO of 3412.6g weight content 40%2Colloidal sol and 6.0g NaOH withAnd 19.6g15 % by weight phosphoric acid,diluted joins in slurry III, mix making beating, regulate the pH value of slurry with rare nitric acid is 1 simultaneously, mustTo slurry IV (solid content 45wt%), by this slurry spray drying forming, spraying machine inlet temperature is 200 DEG C, outlet temperature 100DEG C, then carry out roasting, 400 DEG C of sintering temperatures, roasting time 0.15h, obtains that microspheroidal fluid bed iron-base fischer-tropsch is synthetic urgesAgent, it is made and consists of (except special identifier all components is than being atomic ratio):
30 % by weight Fe100Ba200Co0.5Na10P2Ox+ 70 % by weight SiO2。
[embodiment 3]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 686g barium nitrate and 3.49g six hydration nitreAcid nickel is dissolved in the water and makes solution, then, by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 1550g, this is precipitatedFilter, and by the mixed oxide II that obtains fresh clean barium monoxide and nickel oxide after deionized water cyclic washing, by solution I andMixed oxide II is mixed making beating and is obtained slurry III; By the TiO2 colloidal sol of 472.87g weight content 20% and 13.8g rubidium hydroxideAnd 17.2g15 % by weight phosphoric acid,diluted joins in slurry III, mix making beating, by the pH value of rare nitric acid adjusting slurry be simultaneously2.3, obtain slurry IV (solid content 35wt%), by this slurry spray drying forming, spraying machine inlet temperature is 300 DEG C, outlet temperatureSpend 180 DEG C, then carry out roasting, 450 DEG C of sintering temperatures, roasting time 0.5h, obtains microspheroidal fluid bed iron-base fischer-tropsch and closesBecome catalyst, it is made and consists of (except special identifier all components is than being atomic ratio):
85 % by weight Fe100Ba175Ni0.8Rb9S1.75Ox+ 15 % by weight TiO2。
[embodiment 4]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 2.54g strontium nitrate and 196.3g six hydrationsNickel nitrate is dissolved in the water and makes solution, then by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 389.3g, this is heavyForm sediment and filter, and by the mixed oxide II that obtains fresh clean strontium oxide strontia and nickel oxide after deionized water cyclic washing, by moltenLiquid I is mixed making beating and is obtained slurry III with mixed oxide II; By the TiO2 colloidal sol of 1597g weight content 20% and 0.34g hydroxideCaesium and 0.29g15 weight 15% dilute sulfuric acid join in slurry III, mix making beating, regulate the pH value of slurry with rare nitric acid simultaneouslyBe 1.8, obtain slurry IV (solid content 25wt%), by this slurry spray drying forming, spraying machine inlet temperature is 320 DEG C, outlet190 DEG C of temperature, then carry out roasting, 700 DEG C of sintering temperatures, and roasting time 5h, obtains microspheroidal fluid bed iron-base fischer-tropsch and closesBecome catalyst, it is made and consists of (except special identifier all components is than being atomic ratio):
35 % by weight Fe100Sr0.8Ni45Cs0.15S0.03Ox+ 65 % by weight TiO2。
[embodiment 5]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 2.54g strontium nitrate and 196.3g six hydrationsNickel nitrate is dissolved in the water and makes solution, then by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 389.3g, this is heavyForm sediment and filter, and by the mixed oxide II that obtains fresh clean strontium oxide strontia and nickel oxide after deionized water cyclic washing, by moltenLiquid I is mixed making beating and is obtained slurry III with mixed oxide II; By the TiO2 colloidal sol of 1597g weight content 20% and 0.34g hydroxideCaesium and 0.29g15 weight 15% dilute sulfuric acid and 0.29g15 weight 15% phosphoric acid,diluted join in slurry III, mix making beating, simultaneouslyRegulating the pH value of slurry with weak aqua ammonia is 4.5, obtains slurry IV (solid content 20wt%), by this slurry spray drying forming, and sprayingMachine inlet temperature is 260 DEG C, and then 140 DEG C of outlet temperatures carry out roasting, 500 DEG C of sintering temperatures, and roasting time 5h, obtains micro-Spherical fluid bed iron-base fischer-tropsch synthesis catalyst, it is made and consists of (except special identifier all components is than being atomic ratio):
35 % by weight Fe100Sr0.8Ni45Cs0.15S0.03P0.03Ox+ 65 % by weight TiO2。
[embodiment 6]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 63.5g strontium nitrate and 87.2g six hydration nitreAcid cobalt is dissolved in the water and makes solution, then, by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 375g, this is precipitatedFilter, and by the mixed oxide II that obtains fresh clean strontium oxide strontia and cobalt oxide after deionized water cyclic washing, by solution I andMixed oxide II is mixed making beating and is obtained slurry III; By the TiO of 1570g weight content 20%2Colloidal sol and 4.2g potassium hydroxide and4.83g15 weight 15% dilute sulfuric acid joins in slurry III, mixes making beating, and regulate the pH value of slurry with rare nitric acid is 2.0 simultaneously,Obtain slurry IV (solid content 30wt%), by this slurry spray drying forming, spraying machine inlet temperature is 290 DEG C, outlet temperature170 DEG C, then carry out roasting, 600 DEG C of sintering temperatures, roasting time 3.5h, obtains microspheroidal fluid bed iron-base fischer-tropsch syntheticCatalyst, it is made and consists of (except special identifier all components is than being atomic ratio):
35 % by weight Fe100Sr20Ni20K5S0.5Ox+ 65 % by weight TiO2。
[embodiment 7]
Get 367.43g ironic citrate wiring solution-forming I soluble in water; By molten to 784g barium nitrate and 2.18g cabaltous nitrate hexahydrateIn Xie Yushui, make solution, then by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 1800g, by this sedimentation and filtration, andBy the mixed oxide II that obtains fresh clean barium monoxide and cobalt oxide after deionized water cyclic washing, by solution I with mixOxide II is mixed making beating and is obtained slurry III; By the SiO2 colloidal sol of 1462.5g weight content 40% and 3900g weight content 20%TiO2 colloidal sol and 6.0g NaOH and 19.6g15 % by weight phosphoric acid,diluted join in slurry III, mix making beating, use rare simultaneouslyIt is 4 that ammoniacal liquor regulates the pH value of slurry, obtains slurry IV (solid content 40wt%), by this slurry spray drying forming, spraying machine importTemperature is 270 DEG C, and then 160 DEG C of outlet temperatures carry out roasting, 480 DEG C of sintering temperatures, and roasting time 4.5h, obtains microspheroidalFluid bed iron-base fischer-tropsch synthesis catalyst, it is made and consists of (except special identifier all components is than being atomic ratio):
30 % by weight Fe100Ba200Co0.5Na10P2Ox+ 30 % by weight SiO2+ 40 % by weight TiO2。
[embodiment 8]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 784g barium nitrate and 2.18g six hydration nitreAcid cobalt is dissolved in the water and makes solution, then, by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 1800g, this is precipitatedFilter, and by the mixed oxide II that obtains fresh clean barium monoxide and cobalt oxide after deionized water cyclic washing, by solution I andMixed oxide II is mixed making beating and is obtained slurry III; By the SiO2 colloidal sol of 1462.5g weight content 40% and 3900g weight content20% TiO2 colloidal sol and 6.0g NaOH and 19.6g15 % by weight phosphoric acid,diluted and 19.6g15 weight 15% dilute sulfuric acid joinIn slurry III, mix making beating, regulate the pH value of slurry with rare nitric acid is 1.3 simultaneously, obtains slurry IV (solid content 40wt%), willThis slurry spray drying forming, spraying machine inlet temperature is 360 DEG C, then 220 DEG C of outlet temperatures carry out roasting, sintering temperature650 DEG C, roasting time 4.15h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and it is made and consists of (except specialMark all components is than being atomic ratio):
30 % by weight Fe100Ba200Co0.5Na10S2P2Ox+ 30 % by weight SiO2+ 40 % by weight TiO2。
[embodiment 9]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 63.5g strontium nitrate and 87.2g six hydration nitreAcid cobalt and 20.0g magnesium nitrate hexahydrate are dissolved in the water and make solution, then by molten the 6 % by weight ammoniacal liquor of this solution and 390gLiquid parallel-flow precipitation, by this sedimentation and filtration, and with obtaining fresh clean strontium oxide strontia and cobalt oxide after deionized water cyclic washingMixed oxide II, mixes solution I making beating and obtains slurry III with mixed oxide II; By the TiO of 1570g weight content 20%2Colloidal sol and 4.2g potassium hydroxide and 4.83g15 weight 15% dilute sulfuric acid join in slurry III, mix making beating, use rare nitre simultaneouslyIt is 1 that acid regulates the pH value of slurry, obtains slurry IV (solid content 30wt%), by this slurry spray drying forming, and spraying machine import temperatureDegree is 270 DEG C, and then 160 DEG C of outlet temperatures carry out roasting, 600 DEG C of sintering temperatures, and roasting time 1h, obtains microspheroidal fluidisationBed iron-base fischer-tropsch synthesis catalyst, it is made and consists of (except special identifier all components is than being atomic ratio):
35 % by weight Fe100Sr20Ni20K5Mg5.2S0.5Ox+ 65 % by weight TiO2。
[embodiment 10]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 1.96g barium nitrate and 218.3g six hydrationsCobalt nitrate is dissolved in the water and makes solution, then by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 450g, by this precipitationFilter, and by the mixed oxide II that obtains fresh clean barium monoxide and cobalt oxide after deionized water cyclic washing, by solution IMix making beating with mixed oxide II and obtain slurry III; By the SiO of 49.3g weight content 40%2Colloidal sol and 0.084g potassium hydroxideJoin in slurry III, mix making beating, regulate the pH value of slurry with ammoniacal liquor is 5 simultaneously, obtains slurry IV (solid content 15wt%),By this slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, and then 230 DEG C of outlet temperatures carry out roasting, roasting temperatureSpend 750 DEG C, roasting time 6h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and it is made and consists of (except special markKnow all components than being atomic ratio):
90 % by weight Fe100Ba0.5Co50K0.1Ox+ 10 % by weight SiO2。
[comparative example 1]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; By 1.96g barium nitrate and 218.3g six hydrationsCobalt nitrate is dissolved in the water and makes solution, then by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 450g, by this precipitationFilter, and by the mixed oxide II that obtains fresh clean barium monoxide and cobalt oxide after deionized water cyclic washing, by solution IMix making beating with mixed oxide II and obtain slurry III; By the SiO of 8430.3g weight content 40%2Colloidal sol and 0.084g hydroxidePotassium and 0.098g15 % by weight dilute sulfuric acid join in slurry III, mix making beating, and regulate the pH value of slurry with ammoniacal liquor is 5 simultaneously,Obtain slurry IV (solid content 15wt%), by this slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, outlet temperature230 DEG C, then carry out roasting, 750 DEG C of sintering temperatures, roasting time 6h, obtains that microspheroidal fluid bed iron-base fischer-tropsch is synthetic urgesAgent, it is made and consists of (except special identifier all components is than being atomic ratio):
5 % by weight Fe100Ba0.5Co50K0.1S0.01Ox+ 95 % by weight SiO2。
[comparative example 2]
Get the Fe(NO3)39H2O wiring solution-forming I soluble in water of 606.03g; 218.3g cabaltous nitrate hexahydrate is dissolved in to waterIn make solution, then, by the 6 % by weight ammonia spirit parallel-flow precipitations of this solution and 450g, by this sedimentation and filtration, and use deionizationAfter water cyclic washing, obtain the mixed oxide II of fresh clean barium monoxide and cobalt oxide, by solution I and mixed oxide IIMix making beating and obtain slurry III; By the SiO of 49.3g weight content 40%2Colloidal sol and 0.084g potassium hydroxide and 0.098g15 are heavyAmount % dilute sulfuric acid joins in slurry III, mixes making beating, and regulate the pH value of slurry with ammoniacal liquor is 5 simultaneously, obtains slurry IV (admittedly containAmount 15wt%), by this slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperatures, then roastBurn, 750 DEG C of sintering temperatures, roasting time 6h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and it is made and consists of(except special identifier all components is than being atomic ratio):
90 % by weight Fe100Co50K0.1S0.01Ox+ 10 % by weight SiO2。
[comparative example 3]
Method described in employing CN1395993A is prepared fixed bed catalyst, and its formula is identical with embodiment 1
Preparedly above-mentionedly except comparative example 3, under following reaction condition, carry out Fischer-Tropsch synthesis except catalyst, knotFruit is listed in table 1.
Reducing condition is:
450 DEG C of temperature
Pressure 0.2MPa
50 grams of loaded catalysts
Catalyst loading (reaction volume air speed) 2500 hours-1
Reducing gases H2/CO＝0.25/1
24 hours recovery times
Reaction condition is:
38 millimeters of fluidized-bed reactors of φ
300 DEG C of reaction temperatures
Reaction pressure 1.75MPa
50 grams of loaded catalysts
Catalyst loading (reaction volume air speed) 10000 hours-1
Raw material proportioning (mole) H2/CO＝2/1
By comparative example 3 by described in patent CN1395993A in fixed bed evaluation analysis the results are shown in Table 1
The evaluation result of table 1 embodiment catalyst
22Data while being reacted to 2000h
* select from the data of former patent
Claims (8)
1. for a ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene, in catalyst weight umber, comprise following component:
A) 10～70 parts of carriers, carrier is at least one being selected from the oxide of Si or Ti;
B) 30～90 parts of active components, active component contains with atomic ratio measuring, the composition that chemical formula is following:
Fe100AaBbCcOx
A is selected from the one in Ba or Sr;
B is selected from the one in Co or Ni;
C is selected from the one in alkali metal;
The span of a is 0.5～200.0;
The span of b is 0.1～10.0;
The span of c is 0.1～10.0;
X meets the required oxygen atom sum of each element valence in catalyst.
2. the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene according to claim 1, is characterized in that active componentAlso containing element D, D is at least one of P or S, the ratio of D and Fe is taking atomic ratio measuring as Fe:D=100:d, the span of dBe 0.01～2.0.
3. the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene according to claim 1 and 2, is characterized in that getting of aValue scope is 0.8～175.0.
4. the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene according to claim 1 and 2, is characterized in that getting of cValue scope is 0.15～9.0.
5. the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene according to claim 1 and 2, is characterized in that carrierContent is 15～65 parts.
6. the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene according to claim 2, is characterized in that the value model of dEnclose is 0.03～1.75.
7. the preparation method of the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene claimed in claim 1, comprises following techniqueStep:
(1) by the solution I of making soluble in water soluble ferric iron salt;
(2) will be containing the salt of A component and the salt solution of making soluble in water containing B component, then with alkaline precipitating agent parallel-flow precipitation afterFiltration obtains the mixed oxide II of A and B;
(3) solution I is mixed to making beating with mixed oxide II and obtain slurry III;
(4) will be selected from SiO2Or TiO2In at least one colloidal sol and containing hydroxide or salting liquid and the dilute sulfuric acid of C componentOr at least one of phosphoric acid,diluted join in slurry III, mix making beating, add acid-base modifier to regulate the pH value of slurry is 1 simultaneously～5 obtain slurry IV, and slurry IV solid content is 15～45 % by weight;
(5) slurry IV is sent into spray dryer spray shaping, then 400～750 DEG C of roasting temperatures 0.15～6 hour,Obtain microsphere shaped iron based catalyst.
8. the preparation method of the ferrum-based catalyst for Fischer-Tropsch synthesizing low-carbon alkene according to claim 7, its feature existsBe 200～380 DEG C of inlet temperatures in the spray shaping condition of catalyst, 100～230 DEG C of outlet temperatures; Sintering temperature is 450～700 DEG C, roasting time is 0.5～5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310023095.4A CN103933989B (en) | 2013-01-23 | 2013-01-23 | For the synthesis of the Catalysts and its preparation method of low-carbon alkene |
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| CN104549296B (en) * | 2013-10-28 | 2017-09-15 | 中国石油化工股份有限公司 | Microspheroidal synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof |
| CN105435801B (en) * | 2014-08-27 | 2017-12-15 | 中国石油化工股份有限公司 | Load typed iron catalyst and its preparation method and application |
| CN106607061B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins |
| CN106607050B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins |
| CN106607048B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | The method of fixed bed production low-carbon alkene |
| CN106607051B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | The catalyst and preparation method thereof of one step producing light olefins of synthesis gas |
| CN115475637B (en) * | 2021-06-16 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156809A (en) * | 1999-04-21 | 2000-12-05 | Reema International Corp. | Multiple reactor system and method for fischer-tropsch synthesis |
| CN102452878A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by synthetic gas one-step technology |
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| US6156809A (en) * | 1999-04-21 | 2000-12-05 | Reema International Corp. | Multiple reactor system and method for fischer-tropsch synthesis |
| CN102452878A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by synthetic gas one-step technology |
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