CN109647426A - The ferrum-based catalyst of the direct producing light olefins of synthesis gas - Google Patents

The ferrum-based catalyst of the direct producing light olefins of synthesis gas Download PDF

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CN109647426A
CN109647426A CN201710934756.7A CN201710934756A CN109647426A CN 109647426 A CN109647426 A CN 109647426A CN 201710934756 A CN201710934756 A CN 201710934756A CN 109647426 A CN109647426 A CN 109647426A
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catalyst
synthesis gas
light olefins
ferrum
producing light
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CN109647426B (en
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陶跃武
宋卫林
庞颖聪
李剑锋
戴毅敏
顾丹
顾一丹
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/889—Manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • 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 ferrum-based catalysts of the direct producing light olefins of synthesis gas, mainly solve the problems, such as that selectivity of light olefin is lower in the prior art, the present invention by using the direct producing light olefins of synthesis gas ferrum-based catalyst, the catalyst includes carrier and active component, the active component contains with atomic ratio measuring, the following composition Fe of chemical formula100MnaZnbAcKdOx, wherein A includes selected from least one of IVB element and/or including selected from least one of rare earth element；Carrier dosage is that 30~70% technical solution of catalyst weight preferably solves the problems, such as this by weight percentage, be can be used in the industrial production of fluid bed syngas synthesizing low-carbon alkene.

Description

The ferrum-based catalyst of the direct producing light olefins of synthesis gas
Technical field
The present invention relates to the iron-based catalyst of the direct producing light olefins of synthesis gas, preparation method and applications.
Background technique
It is nineteen twenty-three by Germany scientist Frans that synthesis gas, which is passed through the method that catalyst action is converted into hydro carbons, Fischer and Hans Tropsch invention, heterogeneous catalysis hydrogenation occurs on metallic catalyst for abbreviation F-T synthesis, i.e. CO Reaction generates the process of the mixture based on linear paraffin and alkene.Germany the twenties in last century just carried out research and Exploitation, and industrialization was realized in 1936, it is closed after World War II because can not economically be competed with petroleum industry；South Africa possesses Coal resources abundant, but petroleum resources plaque is weary, and is limited for a long time by international community's economy and political sanction, its hair is forced Coal-to-oil industry technology is opened up, and having built up First production capacity in 1955 is ten thousand tons of product/year coal base F-T synthesis of 25-40 Oily factory (Sasol-1).
1973 and 1979 world oil crisis twice cause world's crude oil price to fall and swing fluctuating, big rise and big fall, It is laid in based on the considerations of Strategic Technology, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, south Non- Sasol company builds up in succession again and Liang Zuomeiji synthetic oil factory of having gone into operation.But World oil price in 1986 plummets, and postpones Heavy industrialization process of the F-T synthetic technology in other countries.
Since twentieth century nineties, petroleum resources shortage and in poor quality, while coal and natural gas proved reserves increasingly But it is continuously increased, F-T synthetic technology attracts extensive attention again.Currently, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world Class, wherein naphtha accounts for major part, and there are also alkane, hydrogenated diesel oil, part mink cell focuses etc..Both at home and abroad mostly with natural gas or lightweight stone Oil distillate is raw material, produces low-carbon alkene using steam cracking process in Ethylene Complex unit, steam cracking is in petrochemical industry Big power consumption device, and be completely dependent on non-renewable petroleum resources, with the growing lack of petroleum resources, be badly in need of finding and replace For resource.So the research work with other substitution of resources petroleum producing olefinic hydrocarbons is gradually paid attention to, it is some famous in the world Oil company and scientific research institutions all carried out the research of this respect, and achieve good achievement.
After decades of development, F-T synthetic catalyst has also obtained significant progress, and fischer-tropsch synthetic catalyst usually wraps Include following component: active metal (the VIIIth group 4 transition metal), oxide carrier or structural promoter (SiO2,Al2O3Deng), chemistry helps Agent (alkali metal oxide, transition metal) and precious metal additive (Ru, Re etc.).Fe largely generates alkene and oxygenatedchemicals, Ru, Co mainly generates long-chain saturated hydrocarbons, and Ni mainly generates methane.When due to Ni compressive reaction easily formed carbonyls be lost with And methanation is serious, Ru, Rh etc. are expensive, currently used catalyst, from active component for be divided into two major classes: it is iron-based Catalyst and cobalt-base catalyst.Co-catalyst influences very big, the raising of selectivity of light olefin for the selectivity of low-carbon alkene It is mainly realized by co-catalyst, the selection of co-catalyst and adding technique are the key technologies for developing excellent catalyst One of.
The direct F-T synthesizing low-carbon alkene of ferrum-based catalyst carries out mostly in fixed bed at present, in patent CN1040397C It is just referred to a kind of ferrum-based catalyst for F- T synthesis low-carbon alkene, the selectivity of low-carbon alkene can be up to 69%.But It is that structure is complicated for fixed bed reactors, expensive, cooling is difficult, and the production capacity of whole device is lower.The spy of fluidized-bed reactor Point is that temperature is higher, and conversion ratio is higher, and there is no the difficulty of solid-liquor separation, product is mostly lower carbon number hydrocarbons；Build and operating cost compared with It is low, and low pressure difference saves a large amount of compression expense, and is more conducive to except the heat released in dereaction, simultaneously because gas Linear velocity is low, and wear problem is smaller, this makes it possible to operate for a long time.The currently reported fluidized bed F-T that is applied to is synthesized Be mostly molten iron type catalyst, as be referred in patent CN1704161A it is a kind of for F-T synthesize molten iron type catalyst；But mesh There are products not enough to concentrate for preceding fluidized bed F-T synthesis, the not high enough problem of the selectivity of low-carbon alkene.
Summary of the invention
The first technical problem to be solved by the present invention is the problem that selectivity of light olefin is lower in the prior art, is provided A kind of ferrum-based catalyst of the direct producing light olefins of synthesis gas, the catalyst have the characteristics that selectivity of light olefin is high.
The second technical problem to be solved by the present invention is the application of above-mentioned catalyst.
The third technical problem to be solved by the present invention is the preparation method of above-mentioned catalyst.
One of to solve above-mentioned technical problem, technical scheme is as follows:
The ferrum-based catalyst of the direct producing light olefins of synthesis gas, the catalyst include carrier and active component, the activity Component contains with atomic ratio measuring, the following composition of chemical formula:
Fe100MnaZnbAcKdOx
Wherein A includes selected from least one of IVB element and/or including selected from least one of rare earth element；
The value range of a is 5.0~60.0 in formula；
The value range of b is；1.0~30.0；
The value range of c is；0.1~50.0；
The value range of d is 0.1~10.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；
Carrier dosage is the 30~70% of catalyst weight by weight percentage.
In above-mentioned technical proposal, carrier is not particularly limited, can be using those of commonly used in the art, such as, but not limited to Including at least one of aluminium oxide, silica and titanium oxide or their mixture.
In above-mentioned technical proposal, IVB element preferably includes Zr.
In above-mentioned technical proposal, the preferred La of rare earth element.
In above-mentioned technical proposal, one of technical solution more preferably, A preferably includes Zr and Ag, and Zr and Ag are being improved There is synergistic effect, at this time the specific chemical formula of the composition in terms of the selectivity of low-carbon alkene are as follows:
Fe100MnaZnbZr1.0~30.0KdAg0.1~10.0Ox
In above-mentioned technical proposal, two, A of technical solution more preferably preferably includes La and Ag, and La and Ag are being improved There is synergistic effect, at this time the specific chemical formula of the composition in terms of the selectivity of low-carbon alkene are as follows:
Fe100MnaZnbKdAg0.1~10.0La0.1~10.0Ox
In above-mentioned technical proposal, three, A of technical solution more preferably preferably includes Zr and La, and Zr and La are being improved There is synergistic effect, at this time the specific chemical formula of the composition in terms of the selectivity of low-carbon alkene are as follows:
Fe100MnaZnbZr1.0~30.0KdLa0.1~10.0Ox
In above-mentioned technical proposal, as most preferred technical solution, A includes Zr, Ag and La simultaneously, at this time Zr, Ag and La There is combination synergy in terms of the selectivity for improving low-carbon alkene, at this time the specific chemical formula of the composition are as follows:
Fe100MnaZnbZr1.0~30.0KdAg0.1~10.0La0.1~10.0Ox。
In above-mentioned technical proposal, the value range of a is preferably 10.0~50.0.Such as, but not limited to 15,25,30,35, 40,45 etc..
In above-mentioned technical proposal, the value range of b is preferably 5.0~25.0.Such as, but not limited to 6.0,7.0,8.0,10, 12,15,20,25 etc..
In above-mentioned technical proposal, the value range of c is preferably 0.1~40.0.Such as, but not limited to 0.2,0.5,1,5,10, 15,20,25,30,35 etc..
In above-mentioned technical proposal, the value range of d is 1.0~8.0.Such as, but not limited to 1.5,2.0,3.0,4.0,5.0, 6.0,7.0,7.5 etc..
Atomic ratio of Zr such as, but not limited to, 1.5,2.0,3.0,5.0,10,15,20,25 etc. in above-mentioned technical proposal
The atomic ratio of Ag such as, but not limited to, 0.5 in above-mentioned technical proposal, 1.0,1.5,2.0,2.5,3.0,4.0,5.0, 6.0,7.0,8.0,9.0 etc..
The atomic ratio of La such as, but not limited to, 0.5 in above-mentioned technical proposal, 1.0,1.5,2.0,2.5,3.0,4.0,5.0, 60,7.0,8.0,9.0 etc..
Catalyst of the present invention for synthesizing low-carbon alkene reaction before can first pass through reduction, can also without reduction, But preferably by reduction.When reduction, reducing condition is not particularly limited, and those skilled in the art can reasonably select, such as But be not limited to the reducing condition of catalyst produced by the present invention: pressure is 0.05~5MPa, preferably 0.1~4MPa；Also Primordial Qi Body can use hydrogen, carbon monoxide or synthesis gas, when with synthesis gas, H2/ CO molar ratio be 0.1~6.0, preferably 0.2~ 6.0；Also the load of Primordial Qi is 100~8000 hours-1, preferably 500~6000 hours-1；Reduction temperature is 200~600 DEG C, Preferably 220~500 DEG C；Recovery time is 1~100 hour, preferably 6~72 hours.
In order to year-on-year, reducing condition used in obtained catalyst is equal in the specific embodiment of the invention are as follows:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours.
To solve above-mentioned technical problem two, technical scheme is as follows:
Catalyst described in any one of technical solution of one of above-mentioned technical problem is anti-in the direct producing light olefins of synthesis gas Application in answering.
Key problem in technology of the invention is the selection of catalyst, can for process conditions those skilled in the art of concrete application It does not need to make the creative labor to reasonably select, such as, but not limited to:
In the presence of the catalyst described in any one of technical solution of one of above-mentioned technical problem, synthesis gas reaction is generated Low-carbon alkene.
One skilled in the art will appreciate that low-carbon alkene refers to the alkene of C2~C4, more particularly ethylene, propylene and butylene Or their mixture.Butylene includes butene-1, butene-2, isobutene, butadiene.
The temperature of reaction, which can be reaction temperature, to be 200~600 DEG C, preferably 220~500 DEG C；
The pressure of reaction can be 0.5~10MPa, preferably 1~8MPa；；
H in synthesis gas2/ CO molar ratio can be 0.1~5.0, preferably 0.5~3.0；
The volume space velocity of synthesis gas can be 100~8000 hours-1, preferably 500~6000 hours-1, more preferably 2000 ~6000 hours-1。
In order to count on year-on-year basis, the evaluation condition of the catalyst used in the specific embodiment of the invention is equal are as follows:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
It is the three of solution present invention problem, technical solution of the present invention is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, including following technique step It is rapid:
Obtain the aqueous solution including the metallic element in addition to K in the composition；
The colloidal sol of aequum carrier is added to above-mentioned aqueous solution, KOH solution is added, adjusts slurry with acid-base modifier PH value is 1~6, obtains slurry；
Slurry is sent into spray dryer spray shaping；
Roasting.
In above-mentioned technical proposal, the temperature of roasting is preferably 400~1000 DEG C, and more preferably 450~800 DEG C.
In above-mentioned technical proposal, the time of roasting is preferably 0.15~10 hour, and more preferably 0.5~8 hour.
In above-mentioned technical proposal, when the composition includes simultaneously La, Zr and Ag, the preparation method can be embodied as It comprises the following steps that:
(1) solution I is made by aequum soluble ferric iron salt is soluble in water,
(2) aequum solubility La salt is dissolved in hot water and solution II is made,
(3) solution III is made by the soluble compound of Mn, Zn, Zr and Ag are soluble in water,
(4) by I solution of solution, II solution, III solution mixing system at mixed solution IV,
(5) colloidal sol of aequum carrier is added in solution IV in 70-100 DEG C of water-bath, is mixed with beating, is added simultaneously KOH solution, adding acid-base modifier and adjusting the pH value of slurry is 1~6, obtains slurry V,
(6) it is sent into spray dryer spray shaping after slurry V being cooled to 20~60 DEG C, then roasts, obtains microspheroidal Fluidized bed iron-base fischer-tropsch synthesis catalyst.
The process conditions of spray drying forming are not particularly limited, and those skilled in the art can reasonably select, and can take Obtain comparable technical effect.Such as, but not limited to spray inlet temperature can be 200~380 DEG C, and outlet temperature can be 100 Spray-dried to be shaped to microspheroidal under conditions of~230 DEG C, finally catalyst is made in roasting.
For convenient for year-on-year, the spray drying condition that the specific embodiment of the invention uses is equal are as follows:
300 DEG C of inlet temperature,
200 DEG C of outlet temperature.
In above-mentioned technical proposal, soluble ferric iron salt can be ferric nitrate or ferric sulfate.
In above-mentioned technical proposal, the soluble compound of Mn, Zn, Zr and Ag can be nitrate, can be analyzed to oxide Salt.
In above-mentioned technical proposal, the atmosphere of roasting is not particularly limited, but preferably oxidizing atmosphere or inert atmosphere, is Economic consideration, more preferably air atmosphere.
In the present invention, unless specifically stated otherwise, the pressure includes that reaction pressure refers both to gauge pressure.
Using catalyst of the invention, at 200~600 DEG C of reaction temperature, 0.5~10MPa of reaction pressure, catalyst loading 100~8000 hours-1, raw material proportioning (mole) H2/ CO=(0.1~5.0): carrying out F-T synthetic reaction under conditions of 1, CO turns Rate is up to 92.3%, and the selectivity of low-carbon alkene achieves preferable technical effect up to 71.8% in reaction product.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
1, catalyst preparation
Take 409.30 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 142.50 gram 50% Manganese nitrate (Mn (NO3)2), 60.27 grams of zinc nitrate (Zn (NO3)2·6H2O) in Yu Tongyi container, add 200g water, stirring and dissolving obtains Material III.
Material I, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains The aqueous solution 50g of 2.04 grams of KOH makes the pH of mixed slurry with concentration for the pH value that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry =6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is spray 300 DEG C of mist machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters of (φ 89 × 1700 Millimeter) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn30Zn20K3.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 2]
1, catalyst preparation
Take 386.60 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 134.20 gram 50% Manganese nitrate (Mn (NO3)2), 24.39 grams of zirconium nitrate (Zr (NO3)4·5H2O), 56.93 grams of zinc nitrate (Zn (NO3)2·6H2O) in same In one container, add 200g water, stirring and dissolving obtains material III.
Material I, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains The aqueous solution 50g of 1.92 grams of KOH makes the pH of mixed slurry with concentration for the pH value that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry =6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is spray 300 DEG C of mist machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters of (φ 89 × 1700 Millimeter) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Zr6.0K3.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 3]
1, catalyst preparation
Take 397.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 138.00 gram 50% Manganese nitrate (Mn (NO3)2), 58.54 grams of zinc nitrate (Zn (NO3)2·6H2) and 9.85 grams of silver nitrate (AgNO O3) Yu Tongyi container It is interior, add 200g water, stirring and dissolving obtains material III.
Material I, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains The aqueous solution 50g of 1.98 grams of KOH makes the pH of mixed slurry with concentration for the pH value that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry =6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is spray 300 DEG C of mist machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters of (φ 89 × 1700 Millimeter) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20K3.0Ag6.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 4]
1, catalyst preparation
Take 379.80 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 16.20 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 131.90 gram of 50% manganese nitrate (Mn (NO3)2)、 55.93 grams of zinc nitrate (Zn (NO3)2·6H2O) in Yu Tongyi container, add 200g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added Aqueous solution 50g containing 1.89 grams of KOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide PH=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 × 1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20La6.0K3.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 5]
1, catalyst preparation
Take 388.40 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 8.30 grams of lanthanum nitrates (La(NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 134.90 gram of 50% manganese nitrate (Mn (NO3)2)、 57.20 grams of zinc nitrate (Zn (NO3)2·6H2) and 4.81 grams of silver nitrate (AgNO O3) in Yu Tongyi container, add 200g water, it stirs molten Solve material III.
Material I, II, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added Aqueous solution 50g containing 1.93 grams of KOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide PH=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 × 1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20K3.0Ag3.0La3.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 6]
1, catalyst preparation
Take 392.00 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 136.10 gram 50% Manganese nitrate (Mn (NO3)2), 12.37 grams of zirconium nitrate (Zr (NO3)4·5H2O), 57.72 grams of zinc nitrate (Zn (NO3)2·6H2O) and 4.85 grams of silver nitrate (AgNO3) in Yu Tongyi container, add 200g water, stirring and dissolving obtains material III.
Material I, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added and contains The aqueous solution 50g of 1.95 grams of KOH makes the pH of mixed slurry with concentration for the pH value that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry =6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is spray 300 DEG C of mist machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters of (φ 89 × 1700 Millimeter) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Zr3.0K3.0Ag3.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 7]
1, catalyst preparation
Take 383.10 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 8.20 grams of lanthanum nitrates (La(NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 133.00 gram of 50% manganese nitrate (Mn (NO3)2)、 12.09 grams of zirconium nitrate (Zr (NO3)4·5H2O), 56.42 grams of zinc nitrate (Zn (NO3)2·6H2O) in Yu Tongyi container, add 200g Water, stirring and dissolving obtain material III.
Material I, II, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added Aqueous solution 50g containing 1.91 grams of KOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide PH=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 × 1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Zr3.0K3.0La3.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
[embodiment 8]
1, catalyst preparation
Take 386.40 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 5.50 grams of lanthanum nitrates (La(NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 134.20 gram of 50% manganese nitrate (Mn (NO3)2)、8.13 Gram zirconium nitrate (Zr (NO3)4·5H2O), 56.91 grams of zinc nitrate (Zn (NO3)2·6H2) and 3.19 grams of silver nitrate (AgNO O3) in same In one container, add 200g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, the silica solution material of 312.50 gram 40% (weight) is added under stiring, is then added Aqueous solution 50g containing 2.57 grams of KOH makes mixed slurry with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide PH=6.0, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, and specific spray drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.Finally internal diameter be 89 millimeters, length be 1700 millimeters (φ 89 × 1700 millimeters) rotary roasting furnace in roasted 2.0 hours in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn30Zn20Zr2.0K3.0Ag2.0La2.0Ox+ 50 weight %SiO2
2, the reduction and evaluation of catalyst
Obtained catalyst is carried out in reducing condition:
400 DEG C of temperature
Pressure 3.0MPa
100 grams of loaded catalyst
Catalyst loading 4000 hours-1
Also Primordial Qi H2/ CO=2/1
Recovery time 24 hours
It is restored, then carries out Fischer-Tropsch synthesis under the following conditions:
38 millimeters of fluidized-bed reactors of φ
330 DEG C of reaction temperature
Reaction pressure 2.0MPa
100 grams of loaded catalyst
Catalyst loading 3000 hours-1
Raw material proportioning (mole) H2/ CO=2/1.
The experimental result of synthetic reaction is listed in table 1.
Table 1

Claims (10)

1. the ferrum-based catalyst of the direct producing light olefins of synthesis gas, which includes carrier and active component, the active group Divide and contain with atomic ratio measuring, the following composition of chemical formula:
Fe100MnaZnbAcKdOx
Wherein A includes selected from least one of IVB element and/or including selected from least one of rare earth element；
The value range of a is 5.0~60.0 in formula；
The value range of b is；1.0~30.0；
The value range of c is；0.1~50.0；
The value range of d is 0.1~10.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；
Carrier dosage is the 30~70% of catalyst weight by weight percentage.
2. the ferrum-based catalyst of the direct producing light olefins of synthesis gas according to claim 1, it is characterised in that the value model of a Enclose is 10.0~50.0.
3. the ferrum-based catalyst of the direct producing light olefins of synthesis gas according to claim 1, it is characterised in that the value model of b Enclose is 5.0~25.0.
4. the ferrum-based catalyst of the direct producing light olefins of synthesis gas according to claim 1, it is characterised in that the value model of c Enclose is 0.1~40.0.
5. the ferrum-based catalyst of the direct producing light olefins of synthesis gas according to claim 1, it is characterised in that the value model of d Enclose is 1.0~8.0.
6. the ferrum-based catalyst of the direct producing light olefins of synthesis gas according to claim 1-5, it is characterised in that Reduction is first passed through before reaction for the direct producing light olefins of synthesis gas.
7. application of claim 1~6 catalyst in the direct reaction for preparing light olefins of synthesis gas.
8. the preparation method of catalyst described in claim 1~6, comprises the following steps that:
Obtain the aqueous solution including the metallic element in addition to K in the composition；
The colloidal sol of aequum carrier is added to above-mentioned aqueous solution, KOH solution is added, the pH value of slurry is adjusted with acid-base modifier It is 1~6, obtains slurry；
Slurry is sent into spray dryer spray shaping；
Roasting.
9. preparation method according to any one of claims 8, it is characterized in that the temperature of roasting is 400~1000 DEG C.
10. preparation method according to any one of claims 8, it is characterized in that the time of roasting is 0.15~10 hour.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112642437A (en) * 2019-10-12 2021-04-13 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN112705216A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN112705218A (en) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4719240A (en) * 1985-07-11 1988-01-12 Exxon Research And Engineering Company Cerium promoted fischer-tropsch catalysts

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4719240A (en) * 1985-07-11 1988-01-12 Exxon Research And Engineering Company Cerium promoted fischer-tropsch catalysts

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112642437A (en) * 2019-10-12 2021-04-13 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN112705218A (en) * 2019-10-24 2021-04-27 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof
CN112705218B (en) * 2019-10-24 2023-11-28 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof
CN112705216A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN112705216B (en) * 2019-10-25 2023-05-02 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas, and preparation method and application thereof

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