CN106607061B - The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins - Google Patents
The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins Download PDFInfo
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Abstract
The fluid catalyst and preparation method thereof that the present invention relates to a kind of for one-step method from syngas producing light olefins, 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 Ti 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: Fe100AaBbCcOx, A is selected from one of Mo or Cr；B is selected from least one of alkaline-earth metal；C is selected from the technical solution of at least one of Rh or Ir, preferably solves the above problem, the industrial production for one-step method from syngas producing light olefins.
Description
Technical field
The fluid catalyst and preparation method thereof that the present invention relates to a kind of for one-step method from syngas producing light olefins
Background technique
Fischer-Tropsch (Fascher-Tropsch) synthesis is that (main component is CO and H using synthesis gas2) in the effect of catalyst
The process of lower synthesis hydrocarbon, is an important channel of coal and natural gas indirect liquefaction.This method is nineteen twenty-three by Germany scientist
Frans Fischer and Hans Tropsch invention, i.e. heterogeneous catalysis hydrogenation occurs on metallic catalyst for CO, raw
At the process of the mixture based on linear paraffin and alkene.
Germany has just carried out the research and development to F- T synthesis in the twenties in last century, and realizes industry in 1936
Change, is closed after World War II because can not economically be competed with petroleum industry；South Africa possesses coal resources abundant, but petroleum resources
Plaque is weary, and is limited for a long time by international community's economy and political sanction, forces it to develop coal-to-oil industry technology, and in 1955
Having built up First production capacity is 25~400,000 tons of product/year coal base F-T synthetic oil factories (Sasol-1).1973 and
World oil crisis twice in 1979 causes world's crude oil price to fall and swings fluctuating, big rise and big fall, is based on Strategic Technology deposit
The considerations of, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol company are again successive
It builds up and Liang Zuomeiji synthetic oil factory of having gone into operation.But plummeting for World oil price in 1986, has postponed F-T synthetic technology at it
The heavy industrialization process of its country.Since twentieth century nineties, petroleum resources shortage and in poor quality, while coal increasingly
It is but continuously increased with natural gas proved reserves, fischer-tropsch technologies attract extensive attention again, and Fiscber-Tropscb synthesis technology has also obtained considerable
Development.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 in recent years, with the rapid development of our country's economy, is growing day by day to the demand of oil product.The characteristics of China's energy is
Rich coal lacks gas oil starvation, and environmental pollution caused by coal directly burns also is taken seriously increasingly.Exploitation is by coal/natural gas through synthesizing
Gas is converted into the process of oil product, not only can reduce to external dependence on the energy, and for solving caused by fire coal
Problem of environmental pollution has great importance.
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 catalyst of new one-step method from syngas producing light olefins is provided.The catalyst is synthesized for fluidized bed
When 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: a kind of low for one-step method from syngas system
The fluid catalyst 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 Ti；
B) 30~90 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula:
Fe100AaBbCcOx
A is selected from one of Cr or Mo；
B is selected from at least one of alkaline-earth metal；
C is selected from least one of Rh or Ir；
The value range of a is 0.5~200.0；
The value range of b is 0.5~20.0；
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 5~150.0, b value preferred scope be 1.0~15.0, c value preferred scope be 0.5~
8.0, d value preferred scope 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 celite 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 soluble A salt and B salt are soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) SiO will be selected from2Or TiO2At least one of colloidal sol and the compound solution of D be added in slurry III, mix
Mashing being closed, while it is 1~5 to obtain slurry IV that acid-base modifier, which is added, to adjust the pH value of slurry, the solid content of slurry IV is 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.
In the spray shaping condition of the catalyst preferred scope of inlet temperature be 200~380 DEG C, outlet temperature it is excellent
Selecting range 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 Rh or Ir in the catalyst according to said method obtained plus hydrogen
Can so that the conversion ratio of catalyst improves, but the effect of Mo or Cr can then inhibit alkene further add hydrogen so that
The amount of alkene is far longer than the amount of alkane in product, and the poisoning of slight S or P are cooperateed with noble metal Rh or Ir, can press down
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 rhodium chloride of the Fe(NO3)39H2O and 0.314g 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 rhodium oxide；The magnesium nitrate hexahydrate of the Chromium nitrate (Cr(NO3)3),nonahydrate of 3.0g and 76.92g is dissolved in the water and is made
Solution II is mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；It is 40% by 46.02g weight content
SiO2Colloidal sol 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
750 DEG C, calcining time 6h, fluidized bed ferrum-based catalyst of the microspheroidal for one-step method from syngas producing light olefins is obtained,
Group, which is made, to be become (except special identifier all components ratio is atomic ratio):
90 weight %Fe100Cr0.5Mg20.0Rh0.1S0.01Ox+ 10 weight %SiO2
[embodiment 2]
The iridous chloride of the Fe(NO3)39H2O and 44.79g 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 yttrium oxide；528g ammonium heptamolybdate and 35.42g calcium nitrate tetrahydrate are 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 TiO for being 20% by 1580g weight content2Colloidal sol adds
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 sprayed
Drying and moulding, spraying machine inlet temperature are 200 DEG C, 100 DEG C of outlet temperature, are then roasted, 450 DEG C of maturing temperature, are roasted
Time 0.15h obtains fluidized bed ferrum-based catalyst of the microspheroidal for one-step method from syngas producing light olefins, composition is made
For (except special identifier all components ratio is atomic ratio):
60 weight %Fe100Mo200.0Ca10.0Ir10.0P2.0Ox+ 40 weight %TiO2
[embodiment 3]
The rhodium chloride of 367.43g ironic citrate and 1.57g 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 rhodium oxide afterwards three times
Mixed precipitation I；30g Chromium nitrate (Cr(NO3)3),nonahydrate and 63.49g strontium nitrate are dissolved in the water, solution II is made, by solution II and mixed
Sediment I is closed to be mixed with beating to obtain colloidal slurry III；By the SiO of 380g weight content 40%2Colloidal sol is added in slurry III,
It is mixed with beating, the dilute sulfuric acid of 15 weight % of 0.294g is then added, while being 3 with the pH value that weak aqua ammonia adjusts slurry, obtain molten
Colloidal dispersion is uniform and places the uniform sizing material IV (solid content 35%) that will not be layered for a long time, which is spray dried to
Type, 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,
Fluidized bed ferrum-based catalyst of the microspheroidal for one-step method from syngas producing light olefins is obtained, group, which is made, to be become (except special
Mark all components ratio is atomic ratio):
50 weight %Fe100Cr5.0Sr20.0Rh0.5S0.03Ox+ 50 weight %SiO2
[embodiment 4]
The rhodium chloride of the Fe(NO3)39H2O and 25.12g 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 rhodium oxide；395.63g ammonium heptamolybdate and 3.92g barium nitrate are dissolved in the water, solution II is made, by solution
II is mixed with beating to obtain colloidal slurry III with mixed sediment I；The SiO for being 40% by 1142g weight content2Colloidal sol and
The TiO that 1715g weight content is 20%2Colloidal sol is added in slurry III, is mixed with beating, and it is dilute that 7.35g15 weight % is then added
Phosphoric acid, 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 be layered it is uniform
Slurry IV (solid content 30%), by the slurry spray drying forming, spraying machine inlet temperature is 280 DEG C, 150 DEG C of outlet temperature,
Then it is roasted, 700 DEG C of maturing temperature, calcining time 0.5h, obtains microspheroidal for one-step method from syngas producing light olefins
Fluidized bed ferrum-based catalyst, be made group become (except special identifier all components ratio be atomic ratio):
30 weight %Fe100Mo150.0Ba1.0Rh8.0P1.75Ox+ 30 weight %TiO2+ 40 weight %SiO2。
[embodiment 5]
The iridous chloride of the Fe(NO3)39H2O and 2.24g 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 iridium；The magnesium nitrate hexahydrate of 263.75g ammonium heptamolybdate and 53.13g calcium nitrate tetrahydrate and 19.23g is molten
Solution II is made in Xie Yushui, is mixed with beating solution I and mixed sediment II to obtain colloidal slurry III；By 1530g weight
The SiO of content 40%2Colloidal sol is added in slurry III, is mixed with beating, and 7.35g15 weight % phosphoric acid,diluted is then added, with dilute nitre
Acid adjust slurry pH value be 3.5, obtain sol form be uniformly dispersed and place for a long time will not be layered uniform sizing material IV (admittedly contain
25%), by the slurry spray drying forming, spraying machine inlet temperature is 330 DEG C to amount, 200 DEG C of outlet temperature, is then roasted
It burns, 450 DEG C of maturing temperature, calcining time 3.4h, the fluidized bed for obtaining microspheroidal for one-step method from syngas producing light olefins is used
Ferrum-based catalyst, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
35 weight %Fe100Mo100.0Ca15.0Mg5.0Ir0.5P1.75Ox+ 65 weight %SiO2
[embodiment 6]
It takes the rhodium chloride of the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g to be dissolved 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 yttrium oxide and rhodium oxide；By six water of 150g Chromium nitrate (Cr(NO3)3),nonahydrate and 19.23g
Conjunction magnesium 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；It will
The TiO of 998.6g weight content 20%2Colloidal sol is added in slurry III, is mixed with beating, and the dilute phosphorus of 7.35g15 weight % is then added
Acid, at the same with weak aqua ammonia adjust slurry pH value be 4.5, obtain sol form be uniformly dispersed and for a long time place will not be layered it is equal
Homogenate IV (solid content 20%) of material, by the slurry spray drying forming, spraying machine inlet temperature is 360 DEG C, outlet temperature 220
DEG C, it is then roasted, 550 DEG C of maturing temperature, calcining time 1.4h, obtains microspheroidal for one-step method from syngas low-carbon alkene
The fluidized bed ferrum-based catalyst of hydrocarbon, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
45 weight %Fe100Cr25.0Mg5.0Rh0.2Ir0.5P1.75Ox+ 55 weight %TiO2
[embodiment 7]
The rhodium chloride of the Fe(NO3)39H2O and 0.314g 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 rhodium oxide；The magnesium nitrate hexahydrate of the Chromium nitrate (Cr(NO3)3),nonahydrate of 3.0g and 76.92g is dissolved in the water and is made
Solution II is mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；It is 40% by 46.02g weight content
SiO2Colloidal sol is added in slurry III, is mixed with beating, and the dilute sulfuric acid and 0.042g15 weight of 15 weight % of 0.098g is then added
% phosphoric acid,diluted is measured, is 3.5 with the pH value that dust technology adjusts slurry, sol form is obtained and is uniformly dispersed and places for a long time and will not be layered
Uniform sizing material IV (solid content 25%), by the slurry spray drying forming, spraying machine inlet temperature is 260 DEG C, outlet temperature
It 130 DEG C, is then roasted, 550 DEG C of maturing temperature, calcining time 4h, obtains microspheroidal for one-step method from syngas low-carbon
The fluidized bed ferrum-based catalyst of alkene, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
90 weight %Fe100Cr0.5Mg20.0Rh0.1S0.01P0.01Ox+ 10 weight %SiO2
[embodiment 8]
The rhodium chloride of the Fe(NO3)39H2O and 0.314g 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 rhodium oxide；The magnesium nitrate hexahydrate of 13.19g ammonium heptamolybdate and 76.92g is dissolved in the water, solution is made,
II, it is mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；By 128.68g weight content 20%TiO2Add
Enter into slurry III, be mixed with beating, the dilute sulfuric acid of 15 weight % of 0.098g 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 fluidized bed ferrum-based catalyst of the microspheroidal for one-step method from syngas producing light olefins, group is made
As (except special identifier all components ratio is atomic ratio):
85 weight %Fe100Mo5.0Mg20.0Rh0.1S0.01Ox+ 15 weight %TiO2
[embodiment 9]
Take the rhodium chloride of the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g 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 yttrium oxide and rhodium oxide；263.75g ammonium heptamolybdate and 53.13g tetra- are hydrated nitre
The magnesium nitrate hexahydrate of sour calcium and 19.23g, which are dissolved in the water, is made solution II, and solution I and mixed sediment II are mixed with beating
Obtain colloidal slurry III；By the SiO of 1530g weight content 40%2Colloidal sol is added in slurry III, is mixed with beating, then plus
Enter 7.35g15 weight % phosphoric acid,diluted, be 4.7 with the pH value that ammonium hydroxide adjusts slurry, obtains sol form and be uniformly dispersed and put for a long time
The uniform sizing material IV (solid content 20%) that will not be layered is set, by the slurry spray drying forming, spraying machine inlet temperature is 350
DEG C, it 215 DEG C of outlet temperature, is then roasted, 650 DEG C of maturing temperature, calcining time 5.2h, obtains microspheroidal for synthesis gas
The fluidized bed ferrum-based catalyst of one-step method producing light olefins, group, which is made, to be become (except special identifier all components ratio is atom
Than):
35 weight %Fe100Mo100.0Ca15.0Mg5.0Ir0.5Rh0.2P1.75Ox+ 65 weight %SiO2
[embodiment 10]
Take the rhodium chloride of the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g 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 yttrium oxide and rhodium oxide；263.75g ammonium heptamolybdate and 53.13g tetra- are hydrated nitre
The magnesium nitrate hexahydrate of sour calcium and 19.23g, which are dissolved in the water, is made solution II, and solution I and mixed sediment II are mixed with beating
Obtain colloidal slurry III；By the SiO of 1530g weight content 40%2Colloidal sol is added in slurry III, is mixed with beating, then plus
The dilute sulfuric acid and 0.042g15 weight % phosphoric acid,diluted for entering 15 weight % of 0.098g are 5 with the pH value that ammonium hydroxide adjusts slurry, obtain
Sol form is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time, which is spray dried to
Type, spraying machine inlet temperature are 380 DEG C, 230 DEG C of outlet temperature, are then roasted, 750 DEG C of maturing temperature, calcining time 6h,
Fluidized bed ferrum-based catalyst of the microspheroidal for one-step method from syngas producing light olefins is obtained, group, which is made, to be become (except special
Mark all components ratio is atomic ratio):
35 weight %Fe100Mo100.0Ca15.0Mg5.0Ir0.5Rh0.2S0.01P0.01Ox+ 65 weight %SiO2
[comparative example 1]
The rhodium chloride of the Fe(NO3)39H2O and 0.314g 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 rhodium oxide；The magnesium nitrate hexahydrate of the Chromium nitrate (Cr(NO3)3),nonahydrate of 3.0g and 76.92g is dissolved in the water and is made
Solution II is mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；It is 40% by 7869.42g weight content
SiO2Colloidal sol is added in slurry III, is mixed with beating, and the dilute sulfuric acid of 15 weight % of 0.098g is then added, is adjusted with ammonium hydroxide
The pH value of slurry 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,
By the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, is then roasted, roasting temperature
750 DEG C, calcining time 6h of degree obtains fluidized bed ferrum-based catalyst of the microspheroidal for one-step method from syngas producing light olefins,
Group, which is made, in it becomes (except special identifier all components ratio is atomic ratio):
5 weight %Fe100Cr0.5Mg20.0Rh0.1S0.01Ox+ 95 weight %SiO2
[comparative example 2]
The rhodium chloride of the Fe(NO3)39H2O and 0.314g 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 rhodium oxide；The Chromium nitrate (Cr(NO3)3),nonahydrate of 3.0g is dissolved in the water, solution II is made, by solution II with mix it is heavy
Starch I is mixed with beating to obtain colloidal slurry III；The SiO for being 40% by 43.02g weight content2Colloidal sol is added in slurry III,
It 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 sol form point
The uniform sizing material IV (solid content 45%) 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 380 DEG C, 230 DEG C of outlet temperature, is then roasted, 750 DEG C of maturing temperature, calcining time 6h is obtained micro-
The spherical fluidized bed ferrum-based catalyst for one-step method from syngas producing light olefins, group, which is made, to be become (except special identifier institute
Having component ratio is atomic ratio):
90 weight %Fe100Cr0.5Rh0.1S0.01Ox+ 10 weight %SiO2
[comparative example 3]:
Take the rhodium chloride of the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g 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 yttrium oxide and rhodium oxide；263.75g ammonium heptamolybdate and 53.13g tetra- are hydrated nitre
The magnesium nitrate hexahydrate of sour calcium and 19.23g, which are dissolved in the water, is made solution II, and solution I and mixed sediment II are mixed with beating
Obtain colloidal slurry III；By the SiO of 1530g weight content 40%2Colloidal sol is added in slurry III, is mixed with beating, and ammonium hydroxide is used
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,
650 DEG C of maturing temperature, calcining time 5.2h, microspheroidal is obtained for the fluidized bed of one-step method from syngas producing light olefins with iron-based
Catalyst, group, which is made, to be become (except special identifier all components ratio is atomic ratio):
35 weight %Fe100Mo100.0Ca15.0Mg5.0Ir0.5Rh0.2Ox+ 65 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 (10)
1. a kind of fluid catalyst for one-step method from syngas producing light olefins, 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 Ti；
B) 30~90 parts of active components, active component contain with atomic ratio measuring, the following composition of chemical formula: Fe100AaBbCcOx
A is selected from one of Cr or Mo；
B is selected from at least one of alkaline-earth metal；
C is selected from least one of Rh or Ir；
The value range of a is 0.5~200.0；
The value range of b is 0.5~20.0；
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.
2. the fluid catalyst according to claim 1 for one-step method from syngas producing light olefins, active component
It also include element D, D is at least one of S or P, and the ratio of D and Fe are Fe:D=100:d, the value range of d with atomic ratio measuring
It is 0.01~2.
3. the fluid catalyst according to claim 1 or 2 for one-step method from syngas producing light olefins, feature exist
In a value range be 5~150.0.
4. the fluid catalyst according to claim 1 or 2 for one-step method from syngas producing light olefins, feature exist
In b value range be 1.0~15.0.
5. the fluid catalyst according to claim 1 or 2 for one-step method from syngas producing light olefins, feature exist
In c value range be 0.5~8.0.
6. the fluid catalyst according to claim 1 or 2 for one-step method from syngas producing light olefins, feature exist
It is optimal to be by weight percentage the 15~65% of catalyst weight in carrier dosage.
7. the fluid catalyst according to claim 2 for one-step method from syngas producing light olefins, it is characterised in that d
Value range be 0.03~1.75.
8. the preparation method of the fluid catalyst as claimed in claim 2 for one-step method from syngas producing light olefins, including
Following processing step:
(1) by Dissolvable Fe salt with celite 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 soluble A salt and B salt are soluble in water；
(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；
(4) SiO will be selected from2Or TiO2At least one of colloidal sol and the compound solution of D be added in slurry III, mixing is beaten
Slurry, while the pH value of acid-base modifier adjusting slurry is added and obtains slurry IV for 1~5, the solid content of slurry IV is 15~45 weights
Measure %；
(5) by slurry IV be sent into spray dryer spray shaping, then 400~750 DEG C roasting temperature 0.15~6 hour,
Obtain micro-spherical catalyst.
9. the preparation method of the fluid catalyst according to claim 8 for one-step method from syngas producing light olefins,
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.
10. the preparation method of the fluid catalyst according to claim 8 for one-step method from syngas producing light olefins,
It is characterized in that maturing temperature is 450~700 DEG C, calcining time is 0.5~5 hour.
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| CN109912373B (en) * | 2017-12-13 | 2022-03-08 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method thereof |
| CN110639486B (en) * | 2018-06-27 | 2022-07-12 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and application of catalyst in preparation of low-carbon olefin from synthesis gas |
| CN111068687B (en) * | 2018-10-18 | 2022-12-09 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof |
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