CN109092317A - The catalyst system of direct preparation of low carbon olefines by synthetic gas - Google Patents
The catalyst system of direct preparation of low carbon olefines by synthetic gas Download PDFInfo
- Publication number
- CN109092317A CN109092317A CN201710473503.4A CN201710473503A CN109092317A CN 109092317 A CN109092317 A CN 109092317A CN 201710473503 A CN201710473503 A CN 201710473503A CN 109092317 A CN109092317 A CN 109092317A
- Authority
- CN
- China
- Prior art keywords
- solution
- water
- slurry
- catalyst system
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to the catalyst systems of direct synthesis gas producing light olefins, mainly solve the problems, such as that selectivity of light olefin is low in the prior art.The present invention uses the catalyst system of direct synthesis gas producing light olefins, and including following component: 1) active component of n mass parts, the active component include with atomic ratio measuring, the following composition of chemical formula: Fe100MoaLabMgcOx；The value range of a is 50.0~200.0；The value range of b is 5.0~20.0；The value range of c is 5.0~20.0；X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；2) 1 mass parts inert: the inert includes being selected from ZrO2And TiO2At least one of；N is greater than 0 and 90 technical solutions below and preferably resolves the above problem, the industrial production suitable for direct synthesis gas producing light olefins.
Description
Technical field
The present invention relates to a kind of catalyst systems for synthesis gas synthesizing low-carbon alkene
Background technique
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 spy of China's energy
Point is that 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 economic cooperation
It is converted into the process of oil product at gas, not only can reduce to external dependence on the energy, and causes for solving fire coal
Problem of environmental pollution have great importance.Preparing low-carbon olefin has direct method and indirect method, so-called direct method
It is exactly the high temperature fischer-tropsch synthesis under specified conditions under i.e. specific catalyst.Fischer-Tropsch (Fascher-Tropsch) synthesis is to utilize
(main component is CO and H to synthesis gas2) under the effect of the catalyst synthesize hydrocarbon process, be the one of coal and natural gas indirect liquefaction
A important channel.This method is to be invented by Germany scientist Frans Fischer and Hans Tropsch nineteen twenty-three, i.e., CO exists
Heterogeneous catalysis hydrogenation occurs on metallic catalyst, generates 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 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 of 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.
Although having some trials that fixed bed applications are used for low-carbon alkene production in high temperature fischer-tropsch, such as Shandong of Germany at present
You, the DaLian, China Chemistry and Physics Institute, but since Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, cooling in reactor
Difficulty, easy temperature runaway make catalyst be easy inactivation, these trials terminate in laboratory stage.Fluidized bed can be very good to overcome solid
These problems existing for fixed bed, but the fluidized bed of the catalyst or precipitation method preparation either prepared using molten iron method is catalyzed
All there is product distribution width, the low disadvantage of selectivity of light olefin at present in agent.
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, easy temperature runaway, and catalyst is made to be easy inactivation and the selection of low-carbon alkene weight
Property low problem, provide a kind of catalyst system of new direct synthesis gas producing light olefins, which has reaction cooling
Fastly, temperature runaway and the high advantage of low-carbon alkene weight selectivities are not easy.
The second technical problem to be solved by the present invention is that above-mentioned catalyst system uses directly in a fluidized bed reactor
Application in the reaction of method preparation of low carbon olefines by synthetic gas.
To solve above-mentioned technical problem one The technical solution adopted by the invention is as follows:
The catalyst system of direct synthesis gas producing light olefins, including following component:
1) active component of n mass parts, the active component are with atomic ratio measuring, the following composition of chemical formula:
Fe100MoaLabMgcOx
The value range of a is 50.0~200.0；
The value range of b is 5.0~20.0；
The value range of c is 5.0~20.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；
2) 1 mass parts inert:
The inert includes being selected from ZrO2And TiO2At least one of；
N is greater than 0 and 90 or less.
In above-mentioned technical proposal, the value range of a is preferably 75.0~150.0.
In above-mentioned technical proposal, the value range of b is preferably 7.5~15.0.
In above-mentioned technical proposal, the value range of c is preferably 7.5~15.0.
In above-mentioned technical proposal, active constituent and inert are preferably respectively made into microballoon by the catalyst system, and
The non-microballoon for being made of one active constituent and inert, we have surprisingly found that, even if ensemble element in catalyst system
Average composition is identical, which also has better selectivity of light olefin namely preferred catalyst system
Are as follows: the catalyst system of synthesis gas synthesizing low-carbon alkene, including following component:
1) the active component micro-spherical particle of n mass parts, the active component are with atomic ratio measuring, the following group of chemical formula
Close object:
Fe100MoaLabMgcOx
The value range of a is 50.0~200.0；
The value range of b is 5.0~20.0；
The value range of c is 5.0~20.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；
2) 1 mass parts inert micro-spherical particle:
The inert includes being selected from ZrO2And TiO2At least one of.
N is greater than 0 and 90 or less.
In above-mentioned technical proposal, the inert micro-spherical particle can be single ZrO2Microballoon or TiO2Microballoon,
It can be ZrO2Microballoon and TiO2The mixture of microballoon, but optimal is ZrO2-TiO2Complex microsphere, Zr and Ti in complex microsphere
There is synergistic effect in terms of the selectivity for improving low-carbon alkene.
ZrO described in above-mentioned technical proposal2-TiO2In complex microsphere, the molar ratio of Zr and Ti are not particularly limited, but excellent
Select 0.1~10.In this molar ratio range, as non limiting example, such as can be 0.3,0.5,0.7,0.9,1,2,3,
4,5,6,7,8,9 etc..
In above-mentioned technical proposal, n preferably 0.5~10.0 as non limiting example, such as can be within this range
1,2,3,4,5,6,7,8,9 etc..
In above-mentioned technical proposal, active constituent microballoon is preferably using the method included the following steps in the catalyst system
Preparation:
(1) using alkaline matter as precipitating reagent, the Fe ion precipitation in Fe (+2 and/or+trivalent) salting liquid is obtained into Fe
Fresh hydrooxidation object precipitating I；
(2) compound of soluble M o is dissolved in water and solution II is made；
(3) solution II is uniformly mixed to obtain slurry III with sediment I；
(4) solution of the solution of La element and Mg element is added in slurry III, is mixed with beating, use pH adjusting agent
It adjusts pH value and obtains slurry IV for 1~5；
(5) slurry IV is sent into spray dryer spray shaping, roasting obtains microspheric catalyst.
In above-mentioned technical proposal, the preferred ammonium hydroxide of pH adjusting agent or nitric acid described in step (4).
In above-mentioned technical proposal, the solid content of slurry IV described in step (4) is 15~45 weight %.Art technology
Personnel, the solid in step (4) refer to 100 DEG C drying to constant weight remaining substance.
In above-mentioned technical proposal, the solution of La element and the solution of Mg element are added in slurry III in step (4)
Addition sequence is not particularly limited, and those skilled in the art can reasonably select first plus add Mg after La, or first plus after Mg add La,
Or both be added simultaneously, can reach the purpose of the present invention and obtain comparable technical effect.
In above-mentioned technical proposal, preferably 400~750 DEG C of the temperature of step (5) described roasting.
In above-mentioned technical proposal, time preferably 0.15~6 hour of step (5) roasting.Unrestricted example in the section
Son can be 0.5 hour, 1 hour, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours etc..
In above-mentioned technical proposal, the atmosphere of step (iii) roasting is preferably oxygenous atmosphere, is that economic consideration is preferably empty
Gas.
In above-mentioned technical proposal, inert microballoon is preferably using the method included the following steps in the catalyst system
Preparation:
(i) by soluble T i salt and/or Zr salt is soluble in water that solution is made；Then and after alkaline precipitating agent cocurrent, separation
It is precipitated；
(ii) above-mentioned precipitating is added to the water to break up to form suspension, adjusts its pH value with nitric acid, stirs to get colloidal sol；
(iii) above-mentioned colloidal sol is sent into spray dryer spray shaping, roasting obtains microspheric inertia ball particle.
In above-mentioned technical proposal, pH described in step (ii) is preferably 1~5.
In above-mentioned technical proposal, the time of stirring described in step (ii) is preferably 0.5~for 24 hours.
In above-mentioned technical proposal, the temperature stirred in step (ii) is preferably 40~100 DEG C.
In above-mentioned technical proposal, the solid content of colloidal sol described in step (ii) is the colloidal sol of 15~45 weight %.Wherein, institute
Solid content is stated with TiO2And ZrO2It is total total.
In above-mentioned technical proposal, preferably 500~1000 DEG C of temperature of step (iii) roasting.
In above-mentioned technical proposal, time 0.15~6 hour of step (iii) roasting.Unrestricted example in the section
It can be 0.5 hour, 1 hour, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours etc..
In above-mentioned technical proposal, the atmosphere of step (iii) roasting is preferably oxygenous atmosphere, is that economic consideration is preferably empty
Gas.
So far, only active component microballoon and inert component microballoon need to be simply mixed in required ratio by those skilled in the art
The catalyst system of each self-contained microballoon of active constituent and inert of the invention can be obtained.
Those skilled in the art are before this generally, it is considered that evenly spread to inert for active component thus by active component
With the mode that inert is taken shape in same microballoon, more only use active constituent at the mode of microballoon, it is possible to reduce catalyst
Coking and carbon distribution improve the stability of catalyst.But we have surprisingly found that, using catalyst system of the invention, catalyst system
Stability it is higher, the conversion ratio of carbon monoxide and the selectivity of low-carbon alkene are higher, the results showed that, caltalyst of the present invention
Inert microballoon in system is not diluents mechanism to active constituent microballoon, because if only simple dilution can't be reduced
Coking and carbon distribution speed, do not influence the stability of catalyst.
In above-mentioned technical proposal, those skilled in the art can rationally determine the process conditions of spray shaping, inlet temperature
Such as, but not limited to 380 DEG C, 350 DEG C, 320 DEG C, 270 DEG C, 235 DEG C, 200 DEG C etc., outlet temperature be such as, but not limited to 230 DEG C,
200 DEG C, 170 DEG C, 135 DEG C, 105 DEG C etc..
It is the two of solution present invention problem, technical scheme is as follows:
Caltalyst described in any one of technical solution of one of above-mentioned technical problem ties up to straight in fluidized-bed reactor
Application in the reaction of connection preparation of low carbon olefines by synthetic gas.
One skilled in the art will appreciate that above-mentioned catalyst system needs H2Reduction treatment could be used for the conjunction of one step of synthesis gas
In reacting at low-carbon alkene, in order to keep preparation of low carbon olefines by synthetic gas reaction more efficient, one skilled in the art will appreciate that can use
Synthesis gas reduction treatment is through H2The catalyst system of reduction treatment.Above-mentioned H2Reduction treatment and/or synthesis gas reduction treatment, can
To be carried out in preparation of low carbon olefines by synthetic gas reaction fluidized-bed reactor used, can also be fluidized in preparation of low carbon olefines by synthetic gas
It is carried out in other outer reactors (being not limited to fluidized bed) of bed reactor.
In above-mentioned technical proposal, H in synthesis gas2It is preferably 0.5~5.0 with CO molar ratio.
In above-mentioned technical proposal, reaction pressure is preferably 1.0~8.0MPa.As understood by those skilled in the art that
Sample, when not specializing reaction pressure is gauge pressure or absolute pressure, pressure of the present invention refers both to gauge pressure.
In above-mentioned technical proposal, reaction temperature is preferably 250~430 DEG C.
In above-mentioned technical proposal, synthesis gas actual volume air speed is preferably 300~1200 hours-1。
H in above-mentioned technical proposal2Reduction treatment, those skilled in the art can rationally determine specific process conditions.
Such as H2The H of reduction treatment2It can be used in the form of sterling, it can also be with other to the H for reacting inert gas dilution2Shape
Formula uses.Those skilled in the art will know that reacting which inert gas has, such as, but not limited to N2, inert gas etc.
Deng.
H2The pressure of reduction treatment can be 0.1~8.0MPa；H2The temperature of reduction treatment can be 350~500 DEG C；H2
The true empty-running speed of reduction treatment can be 300~1200 hours-1；H2The time of reduction treatment can be 6~24 hours.
In above-mentioned technical proposal, about the process conditions of synthesis gas reduction treatment, those skilled in the art can rationally really
It is fixed.Such as, but not limited to:
H in the synthesis gas of use2/ CO molar ratio ratio can be 0~2.0；
The pressure of synthesis gas reduction treatment can be 0.1~8.0MPa；
The temperature of synthesis gas reduction treatment can be 350~500 DEG C；
The true empty-running speed of synthesis gas reduction treatment is 300~1200 hours-1；
0~48h is handled under conditions of synthesis gas reduction treatment.
In above-mentioned technical proposal, the low-carbon alkene, those skilled in the art will know that referring to C2~C4Alkene, often indicate
For C2 =~C4 =。
Invention catalyst system is used for the conversion ratio of synthesis gas synthesizing low-carbon alkene CO up to 98%, C2 =-C4 =Component
Weight selectivities are up to 73%, and when long-term operation 3000h, there is no failure, reactor tables for active catalyst system
Now as before.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La10Mg10Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4It is dissolved in water, is made into the Ti solution of 0.2mol/L, by the ammonium hydroxide of the solution and 1500g 5wt%
It is separated after parallel-flow precipitation, is washed with deionized and obtains fresh precipitating afterwards three times, by the Ti (OH)4Precipitating is added water and breaks up shape
At the suspension of solid content 25wt%, dilute HNO of 5mol/L is then used3The pH value for adjusting the suspension is 2.5, is stirred at 70 DEG C
16h is mixed, TiO is obtained2Colloidal sol；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；
Then it is roasted, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Catalyst is restored using local reduction way, is directly restoring reactor used middle cut process conditions after reduction
Synthetic reaction condition is changed to start to react；
Reactor specification: 38 millimeters of fluidized-bed reactors of φ；
Loaded catalyst: 50 grams；
Reducing condition are as follows: 450 DEG C of temperature
Pressure 0.5MPa
Catalyst loading (reaction actual volume air speed) 1000 hours-1
Also 1 H of Primordial Qi2
Recovery time 1 12 hours
Also 2 H of Primordial Qi2/ CO=0.5/1
Recovery time 2 24 hours
Synthetic reaction condition are as follows: 350 DEG C of reaction temperature
Reaction pressure 4.0MPa
Catalyst loading (reaction actual volume air speed) 800 hours-1
Raw material proportioning (mole) H2/ CO=1/1
Reaction operation 3000 hours.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 2]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La10Mg10Ox。
2), the preparation of microspheroidal inert particle
Take the Zr (NO of 1mol3)4·5H2O is dissolved in water, is made into the Zr solution of 0.2mol/L, by the solution and 1500g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Zr (OH) afterwards three times4Precipitating, by the Zr
(OH)4Precipitating is added water and breaks up the suspension suspension to form solid content 25wt%, then uses dilute HNO of 5mol/L3It is outstanding to adjust this
The pH value of turbid is 2.5, stirs 16h at 70 DEG C, obtains ZrO2Colloidal sol；It is 280 DEG C by spraying machine inlet temperature, outlet temperature
160℃；Then it is roasted, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 3]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La10Mg10Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4It is dissolved in water, is made into the Ti solution of 0.2mol/L, by the ammonium hydroxide of the solution and 1500g 5wt%
It is separated after parallel-flow precipitation, is washed with deionized and obtains fresh Ti (OH) afterwards three times4Precipitating, by the Ti (OH)4Water is added in precipitating
The suspension to form solid content 25wt% is broken up, dilute HNO of 5mol/L is then used3The pH value for adjusting the suspension is 2.5,70
16h is stirred at DEG C, obtains TiO2Colloidal sol；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, outlet temperature
160℃；Then it is roasted, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle i.
Take the Zr (NO of 1mol3)4·5H2O is dissolved in water, is made into the Zr solution of 0.2mol/L, by the solution and 1500g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Zr (OH) afterwards three times4Precipitating, by the Zr
(OH)4Precipitating is added water and breaks up the suspension suspension to form solid content 25wt%, then uses dilute HNO of 5mol/L3It is outstanding to adjust this
The pH value of turbid is 2.5, stirs 16h at 70 DEG C, obtains ZrO2Colloidal sol；It is 280 DEG C by spraying machine inlet temperature, outlet temperature
160℃；Then it is roasted, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle ii.
3) the active constituent particle of 60g and the inert particle ii of inert the particle i and 20g of 20g, is taken to mix
To required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 4]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La10Mg10Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4With the Zr (NO of 0.65mol3)4·5H2O is dissolved in water, is made into the mixed of the Ti and Zr of 0.2mol/L
Close solution, by being separated after the solution and the ammonium hydroxide parallel-flow precipitation of 2475g 5wt%, be washed with deionized obtain afterwards three times it is fresh
Ti/Zr precipitating, which is precipitated and water is added breaks up to form the suspension of solid content 25wt%, it is then dilute with 5mol/L
HNO3The pH value for adjusting the suspension is 2.5, stirs 16h at 70 DEG C, obtains ZrO2-TiO2Complex sol (TiO2With ZrO2Weight
Amount is than for 1)；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；Then it is roasted
It burns, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[comparative example 1]
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La10Mg10Ox。
Evaluating catalyst:
Evaluation method such as embodiment 1.
In addition in order to reach identical fluidisation state so as to preferably on year-on-year basis and use 23 millimeters of fluidized-bed reactors of φ with
Outside, evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[comparative example 2]
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L；Take the TiOSO of 0.92mol4
With the Zr (NO of 0.60mol3)4·5H2O is dissolved in water, is made into the mixed solution of the Ti and Zr of 0.2mol/L；By above two solution
Be mixed to get the mixed solution of Fe, Ti and Zr, will be separated after the solution and the ammonium hydroxide parallel-flow precipitation of 3600g 5wt%, spend from
Sub- water washing obtains the mixed precipitation I of fresh Fe, Ti, Zr afterwards three times；Take (the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in
Water is made into the solution II of 40wt%；Stirred in water bath 3h after solution II is mixed with sediment I at 80 DEG C obtains slurry III；It will
La (the NO of 0.1mol3)3·6H2O is dissolved in the La Element Solution that water is made into 40wt%；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in
Water is made into the Mg Element Solution of 40wt%；Slurry III is heated to 70 DEG C in 70 DEG C of water-bath, then by above-mentioned La element
Solution and Mg Element Solution are added sequentially in the slurry III after heating in the state that slurry is stirred；In 70 DEG C of condition
Under be mixed with beating, while be added water adjust slurry solid content be 40%；Finally use the HNO of 20wt%3Adjust the pH value of slurry
It is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine inlet temperature is 320 DEG C, 190 DEG C of outlet temperature；Then
It is roasted, 600 DEG C of maturing temperature, calcining time 3h, obtains microspheroidal fluidized bed active constituent particle, composition is made
Are as follows:
60wt%Fe100Mo100La10Mg10Ox+ 40wt%ZrO2-TiO2Compound (TiO2With ZrO21) weight ratio is.
Evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 5]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.72mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；80 after solution II is mixed with sediment I
DEG C stirred in water bath 3h obtain slurry III；By the La (NO of 0.2mol3)3·6H2O be dissolved in water be made into 40wt% La element it is molten
Liquid；By the Mg (NO of 0.2mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry III in 70 DEG C of water-bath
70 DEG C are heated to, is then added sequentially to above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Finally
With the HNO of 20wt%3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import temperature
Degree is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h, obtains microspheroidal fluidisation
Bed active constituent particle, is made composition are as follows: Fe100Mo100La20Mg20Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4With the Zr (NO of 0.65mol3)4·5H2O is dissolved in water, is made into the mixed of the Ti and Zr of 0.2mol/L
Close solution, by being separated after the solution and the ammonium hydroxide parallel-flow precipitation of 2475g 5wt%, be washed with deionized obtain afterwards three times it is fresh
Ti/Zr precipitating, which is precipitated and water is added breaks up to form the suspension of solid content 25wt%, it is then dilute with 5mol/L
HNO3The pH value for adjusting the suspension is 2.5, stirs 16h at 70 DEG C, obtains ZrO2-TiO2Complex sol (TiO2With ZrO2Weight
Amount is than for 1)；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；Then it is roasted
It burns, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 6]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.286mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.05mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.05mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；It will slurry in 70 DEG C of water-bath
Material III is heated to 70 DEG C, then successively adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
Enter in the slurry to after heating III；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；
Finally use the HNO of 20wt%3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine into
Mouth temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal
Fluidized bed active constituent particle, is made composition are as follows: Fe100Mo200La5.0Mg5.0Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4With the Zr (NO of 0.65mol3)4·5H2O is dissolved in water, is made into the mixed of the Ti and Zr of 0.2mol/L
Close solution, by being separated after the solution and the ammonium hydroxide parallel-flow precipitation of 2475g 5wt%, be washed with deionized obtain afterwards three times it is fresh
Ti/Zr precipitating, which is precipitated and water is added breaks up to form the suspension of solid content 25wt%, it is then dilute with 5mol/L
HNO3The pH value for adjusting the suspension is 2.5, stirs 16h at 70 DEG C, obtains ZrO2-TiO2Complex sol (TiO2With ZrO2Weight
Amount is than for 1)；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；Then it is roasted
It burns, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 7]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.2mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.1mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La20Mg10Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4With the Zr (NO of 0.65mol3)4·5H2O is dissolved in water, is made into the mixed of the Ti and Zr of 0.2mol/L
Close solution, by being separated after the solution and the ammonium hydroxide parallel-flow precipitation of 2475g 5wt%, be washed with deionized obtain afterwards three times it is fresh
Ti/Zr precipitating, which is precipitated and water is added breaks up to form the suspension of solid content 25wt%, it is then dilute with 5mol/L
HNO3The pH value for adjusting the suspension is 2.5, stirs 16h at 70 DEG C, obtains ZrO2-TiO2Complex sol (TiO2With ZrO2Weight
Amount is than for 1)；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；Then it is roasted
It burns, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
[embodiment 8]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.143mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.2mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；By slurry in 70 DEG C of water-bath
III is heated to 70 DEG C, then sequentially adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
In slurry III after to heating；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；Most
The HNO of 20wt% is used afterwards3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine import
Temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal stream
Change bed active constituent particle, composition is made are as follows: Fe100Mo100La10Mg20Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4With the Zr (NO of 0.65mol3)4·5H2O is dissolved in water, is made into the mixed of the Ti and Zr of 0.2mol/L
Close solution, by being separated after the solution and the ammonium hydroxide parallel-flow precipitation of 2475g 5wt%, be washed with deionized obtain afterwards three times it is fresh
Ti/Zr precipitating, which is precipitated and water is added breaks up to form the suspension of solid content 25wt%, it is then dilute with 5mol/L
HNO3The pH value for adjusting the suspension is 2.5, stirs 16h at 70 DEG C, obtains ZrO2-TiO2Complex sol (TiO2With ZrO2Weight
Amount is than for 1)；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；Then it is roasted
It burns, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.
3) the inert particle of the active constituent particle and 40g that, take 60g is mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1
[embodiment 9]:
1), the preparation of microspheroidal active constituent particle
Take the Fe (NO of 1mol3)3·9H2O is soluble in water, is made into the Fe solution of 0.5mol/L, by the solution and 1350g
It is separated after the ammonium hydroxide parallel-flow precipitation of 5wt%, is washed with deionized and obtains fresh Fe (OH) afterwards three times3Precipitating I；It takes
(the NH of 0.215mol4)6Mo7O24·4H2O is dissolved in the solution II that water is made into 40wt%；After solution II is mixed with sediment I
80 DEG C of stirred in water bath 3h obtains slurry III；By the La (NO of 0.1mol3)3·6H2O is dissolved in the La element that water is made into 40wt%
Solution；By the Mg (NO of 0.05mol3)2·6H2O is dissolved in the Mg Element Solution that water is made into 40wt%；It will slurry in 70 DEG C of water-bath
Material III is heated to 70 DEG C, then successively adds above-mentioned La Element Solution and Mg Element Solution in the state that slurry is stirred
Enter in the slurry to after heating III；It is mixed with beating under conditions of 70 DEG C, while it is 40% that water, which is added, to adjust the solid content of slurry；
Finally use the HNO of 20wt%3The pH value for adjusting slurry is 5, obtains slurry IV；By IV spray drying forming of slurry, spraying machine into
Mouth temperature is 320 DEG C, 190 DEG C of outlet temperature；Then it is roasted, 600 DEG C of maturing temperature, calcining time 3h obtains microspheroidal
Fluidized bed active constituent particle, is made composition are as follows: Fe100Mo150La10Mg5.0Ox。
2), the preparation of microspheroidal inert particle
Take the TiOSO of 1mol4With the Zr (NO of 0.65mol3)4·5H2O is dissolved in water, is made into the mixed of the Ti and Zr of 0.2mol/L
Close solution, by being separated after the solution and the ammonium hydroxide parallel-flow precipitation of 2475g 5wt%, be washed with deionized obtain afterwards three times it is fresh
Ti/Zr precipitating, which is precipitated and water is added breaks up to form the suspension of solid content 25wt%, it is then dilute with 5mol/L
HNO3The pH value for adjusting the suspension is 2.5, stirs 16h at 70 DEG C, obtains ZrO2-TiO2Complex sol (TiO2With ZrO2Weight
Amount is than for 1)；By the aerosol spray drying and moulding, spraying machine inlet temperature is 280 DEG C, 160 DEG C of outlet temperature；Then it is roasted
It burns, 400 DEG C of maturing temperature, calcining time 2h, obtains microspheroidal fluidized bed inert particle.3) active constituent of 60g, is taken
The inert particle of particle and 40g are mixed to get required catalyst system.
4), evaluating catalyst:
Evaluation method such as embodiment 1.
The experimental result that obtained catalyst system carries out synthetic reaction is listed in table 1.
Table 1
*For the data for being reacted to 2000h.
Claims (9)
1. the catalyst system of direct synthesis gas producing light olefins, including following component:
1) active component of n mass parts, the active component include with atomic ratio measuring, the following composition of chemical formula:
Fe100MoaLabMgcOx；
The value range of a is 50.0~200.0；
The value range of b is 5.0~20.0；
The value range of c is 5.0~20.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；
2) 1 mass parts inert:
The inert includes being selected from ZrO2And TiO2At least one of；
N is greater than 0 and 90 or less.
2. catalyst system according to claim 1, it is characterised in that the value range of a is 75.0~150.0.
3. catalyst system according to claim 1, it is characterised in that the value range of b is 7.5~15.0.
4. catalyst system according to claim 1, it is characterised in that the value range of c is 7.5~15.0.
5. it is anti-that caltalyst described in Claims 1 to 4 ties up to direct synthesis gas producing light olefins in fluidized-bed reactor
Application in answering.
6. application according to claim 5, it is characterized in that H in synthesis gas2It is 0.5~5.0 with CO molar ratio.
7. application according to claim 5, it is characterized in that reaction pressure is 1.0~8.0MPa.
8. application according to claim 5, it is characterized in that reaction temperature is 250~430 DEG C.
9. application according to claim 5, it is characterized in that synthesis gas actual volume air speed is 300~1200 hours-1Item
Under part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710473503.4A CN109092317B (en) | 2017-06-21 | 2017-06-21 | Catalyst system for preparing low-carbon olefin by directly synthesizing gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710473503.4A CN109092317B (en) | 2017-06-21 | 2017-06-21 | Catalyst system for preparing low-carbon olefin by directly synthesizing gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109092317A true CN109092317A (en) | 2018-12-28 |
| CN109092317B CN109092317B (en) | 2021-03-26 |
Family
ID=64795992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710473503.4A Active CN109092317B (en) | 2017-06-21 | 2017-06-21 | Catalyst system for preparing low-carbon olefin by directly synthesizing gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109092317B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371155A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Iron-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its preparation method |
| CN103962148A (en) * | 2013-01-29 | 2014-08-06 | 中国石油化工股份有限公司 | Fluidized bed catalyst for directly preparing low-carbon olefins from synthesis gas and producing method thereof |
| CN104226329A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof |
| CN104549325A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst |
| CN106607061A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing low-carbon olefin from synthetic gas through one step method and preparation method of fluidized bed catalyst |
-
2017
- 2017-06-21 CN CN201710473503.4A patent/CN109092317B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371155A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Iron-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its preparation method |
| CN103962148A (en) * | 2013-01-29 | 2014-08-06 | 中国石油化工股份有限公司 | Fluidized bed catalyst for directly preparing low-carbon olefins from synthesis gas and producing method thereof |
| CN104226329A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof |
| CN104549325A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst |
| CN106607061A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing low-carbon olefin from synthetic gas through one step method and preparation method of fluidized bed catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109092317B (en) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104549296B (en) | Microspheroidal synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof | |
| CN102371155B (en) | Iron-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its preparation method | |
| CN104226329B (en) | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof | |
| CN102371154B (en) | Iron-based catalyst for synthesizing light hydrocarbon and preparation method thereof | |
| CN106607037B (en) | GTO catalyst for fluid bed and preparation method thereof | |
| CN106607053B (en) | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof | |
| CN106607050B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN109092321A (en) | The catalyst system of one-step method from syngas producing light olefins | |
| CN104107699B (en) | Ferrum-based catalyst for synthesizing low-carbon alkene and preparation method thereof | |
| CN106607051B (en) | The catalyst and preparation method thereof of one step producing light olefins of synthesis gas | |
| CN106607061B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN106607058B (en) | Iron-based catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method thereof | |
| CN102039135B (en) | Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN111068687B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof | |
| CN109647426A (en) | The ferrum-based catalyst of the direct producing light olefins of synthesis gas | |
| CN109092322A (en) | The catalyst system of the direct producing light olefins of synthesis gas | |
| CN106607049B (en) | Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof | |
| CN109092317A (en) | The catalyst system of direct preparation of low carbon olefines by synthetic gas | |
| CN103418393A (en) | Catalyst for Fischer-Tropsch synthetic heavy hydrocarbons and preparation method thereof | |
| CN109092316A (en) | The catalyst system of synthesis gas synthesizing low-carbon alkene | |
| CN106607059A (en) | Fe-Mn-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of Fe-Mn-based catalyst | |
| CN102039133A (en) | Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof | |
| CN111068689B (en) | Catalyst for preparing low-carbon olefin by direct synthesis gas method and application thereof | |
| CN103521238B (en) | Micro spherical Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN103657676B (en) | Microspherical Fischer-Tropsch catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |