CN109647428A - The ferrum-based catalyst of one-step method from syngas producing light olefins - Google Patents

The ferrum-based catalyst of one-step method from syngas producing light olefins Download PDF

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CN109647428A
CN109647428A CN201710941271.0A CN201710941271A CN109647428A CN 109647428 A CN109647428 A CN 109647428A CN 201710941271 A CN201710941271 A CN 201710941271A CN 109647428 A CN109647428 A CN 109647428A
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CN109647428B (en
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陶跃武
庞颖聪
李剑锋
宋卫林
戴毅敏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J23/70—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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • 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
    • 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

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Abstract

The present invention relates to the ferrum-based catalysts of one-step method from syngas producing light olefins, mainly solve the problems, such as that selectivity of light olefin is lower in the prior art, the present invention by using one-step method from syngas producing light olefins ferrum-based catalyst, including carrier and active component, the active component contains with atomic ratio measuring, the following composition of chemical formula: Fe100MnaZnbCucQfOx, Q includes that the technical solution selected from least one of lanthanide series preferably solves the problems, such as this, be can be used in the industrial production of fluid bed syngas synthesizing low-carbon alkene.

Description

The ferrum-based catalyst of one-step method from syngas producing light olefins
Technical field
The present invention relates to the ferrum-based catalysts of one-step method from syngas producing light olefins.
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.
According to the difference of used catalyst and the difference of target product, it is anti-that F-T synthesis reactor is divided into fixed bed again Answer device, fluidized-bed reactor and paste state bed reactor.Structure is complicated for fixed bed reactors, expensive, and cooling is difficult, entire to fill The production capacity set is lower.The characteristics of slurry bed system is that reaction temperature is lower, easily controllable, but conversion ratio is lower, and product is mostly high-carbon hydrocarbon And in reactor slurries solid-liquor separation it is more difficult.The characteristics of fluidized-bed reactor is that temperature is higher, and conversion ratio is higher, does not deposit In the difficulty of solid-liquor separation, product is mostly lower carbon number hydrocarbons；It builds and operating cost is lower, and low pressure difference saves a large amount of pressure Contracting expense, and be more conducive to except the heat released in dereaction, simultaneously because gas linear velocity is low, wear problem is smaller, this makes to grow Phase operating is possibly realized.
Iron catalyst have the advantages that it is very much, such as obtain low-carbon alkene with high selectivity, prepare high-octane gasoline etc., In addition ferrum-based catalyst also has the characteristics that operating condition is wide, product adjustability is big.The preparation method of Fe-series catalyst mainly has Three kinds: the precipitation method (precipitated catalyst), ingredient is in addition to Fe, and there are also the auxiliary agents such as Cu, Co, K, it is made into mixing by a certain percentage Solution after being heated to boiling, is added precipitating reagent stirring, is then filtered, washed.Gained filter cake is added into water pulp again, it is fixed to be added Then the potassium silicate of amount, grinds, sieves through drying, extrusion forming；Sintering process (sintered catalyst)；Oxide mixing method is (molten Iron catalyst), raw material is made with the mill scale or magnetite powder of steel rolling mill, adds auxiliary agent A l2O3, MgO, CuO and CuO etc., be sent into 1500 The melting of DEG C electric arc furnaces, the fusant of outflow is through mold, cooling, multiple stage crushing.
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 one-step method from syngas producing light olefins, 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 one-step method from syngas producing light olefins, including carrier and active component, the active component contain Have with atomic ratio measuring, the following composition of chemical formula:
Fe100MnaZnbCucQfOx；
Q includes selected from least one of lanthanide series；
The value range of a is 5.0~60.0；
The value range of b is 5.0~60.0；
The value range of c is 1.0~30.0；
The value range of f is 0.9~40.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst.
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.
In above-mentioned technical proposal, the dosage of carrier is not particularly limited, and those skilled in the art can reasonably select and not With making the creative labor, such as, but not limited to carrier dosage is the 30~70% of catalyst weight by weight percentage
In above-mentioned technical proposal, it is also preferable to include at least one of IA elements by Q, and lanthanide series and alkali metal element are simultaneously There are be conducive to improve the selectivity of low-carbon alkene.At this point, Fe100MnaZnbCucQfOxIt can be further represented as Fe100MnaZnbCucAdLeOx, wherein A is at least one of IA element, and L is at least one of lanthanide series, the value model of d Enclosing for the value range of 1.0~30.0, e is 0.1~10.0.
In above-mentioned technical proposal, the value range of a is preferably 10.0~50.0.Such as, but not limited to 15.0,20.0, 25.0,30.0,35.0,40.0,45.0 etc..
In above-mentioned technical proposal, the value range of b is preferably 10.0~50.0.Such as, but not limited to 15.0,20.0, 25.0,30.0,35.0,40.0,45.0 etc..
In above-mentioned technical proposal, the value range of c is preferably 5.0~25.0.Such as, but not limited to 10.0,12.0,13.0, 14.0,15.0,16.0,17.0,18.0,19.0,20.0 etc..
In above-mentioned technical proposal, the value range of d is preferably 2.0~25.0.Such as, but not limited to 3.0,4.0,5.0, 8.0,10.0,15.0,20.0 etc..
In above-mentioned technical proposal, the value range of e is preferably 1.0~8.0.Such as, but not limited to 2.0,3.0,4.0,5.0, 6.0,7.0 etc..
In above-mentioned technical proposal, the IA element is selected from least one of Li, Na, K and Cs；The IA element is more preferable It simultaneously include at least two in Li, K and Cs, at this time between described two elements, such as Li is being mentioned with K, Li and Cs, K and Cs There is synergistic effect in terms of high-low carbon olefine selective.The atomic ratio between two kinds of elements is not particularly limited at this time, such as but Be not limited to 0.1~10, wherein more specific atomic ratio can be 0.2,0.4,0.6,0.8,1.0,1.5,2.0,2.5,3.0, 3.5,4.0,4.5,5.0 etc..
In above-mentioned technical proposal, the lanthanide series includes being selected from La.
Catalyst of the present invention, can also not for that can first pass through reduction before the reaction of one-step method from syngas producing light olefins By reduction, but preferably by reduction.When reduction, reducing condition is not particularly limited, and those skilled in the art can be reasonable Selection, the reducing condition of catalyst such as, but not limited to produced by the present invention: pressure be 0.05~5MPa, preferably 0.1~ 4MPa；Reducing gas can use hydrogen, carbon monoxide or synthesis gas, when with synthesis gas, H2/ CO molar ratio is 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 in one-step method from syngas producing light olefins Application in reaction.
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:
The slurry including catalyst carrier and active component element is obtained, the pH value of slurry is 1~6；
Slurry is sent into spray dryer spray shaping；
Roasting.
When in active component simultaneously containing lanthanide series with alkali metal element, the preparation method of catalyst is preferably comprised Following processing step:
Obtain the aqueous solution including the metallic element in addition to alkali metal in the composition；
The colloidal sol of aequum carrier is added to above-mentioned aqueous solution, alkali hydroxide soln is added, uses acid-base accommodation It is 1~6 that agent, which adjusts pH value, 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.
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, Cu and lanthanide series can be nitrate, can be analyzed to The salt of oxide.
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 91.7%, and the selectivity of low-carbon alkene achieves preferable technical effect up to 71.5% in reaction product.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
1, catalyst preparation
Take 343.00 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.20 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 119.10 gram of 50% manganese nitrate (Mn (NO3)2)、 30.46 grams of copper nitrate (Cu (NO3)2·3H2) and 50.51 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g Water, stirring and dissolving obtain 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 6.83 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 %Fe100Mn40Zn20Cu15K12La5Ox+ 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 352.10 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.60 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 122.20 gram of 50% manganese nitrate (Mn (NO3)2)、 31.26 grams of copper nitrate (Cu (NO3)2·3H2) and 51.84 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g Water, stirring and dissolving obtain 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 7.09 grams of LiOH 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 %Fe100Mn40Zn20Cu15Li12La5Ox+ 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 319.10 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 11.40 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 110.80 gram of 50% manganese nitrate (Mn (NO3)2)、 28.33 grams of copper nitrate (Cu (NO3)2·3H2) and 46.99 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g Water, stirring and dissolving obtain 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 CsOH 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 %Fe100Mn40Zn20Cu15Cs12La5Ox+ 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 347.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.40 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 120.70 gram of 50% manganese nitrate (Mn (NO3)2)、 30.85 grams of copper nitrate (Cu (NO3)2·3H2) and 51.17 grams of zinc nitrate (Zn (NO O3)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 4.10 grams of NaOH 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, specific spray drying condition in spray dryer after being sufficiently stirred It 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 %Fe100Mn40Zn20Cu15Na12La5Ox+ 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 347.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.40 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 120.70 gram of 50% manganese nitrate (Mn (NO3)2)、 30.85 grams of copper nitrate (Cu (NO3)2·3H2) and 51.17 grams of zinc nitrate (Zn (NO O3)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 3.50 grams of LiOH, 3.46 grams of KOH is that 27% (weight) ammonium hydroxide adjusts the pH value of above-mentioned slurry and makes with concentration The pH=6.0 of mixed slurry is obtained, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, specific to spray Mist drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millis It is roasted 2.0 hours in the rotary roasting furnace of rice (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured catalyst composition Are as follows:
50 weight %Fe100Mn40Zn20Cu15Li6K6La5Ox+ 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 334.80 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 11.90 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 116.20 gram of 50% manganese nitrate (Mn (NO3)2)、 29.73 grams of copper nitrate (Cu (NO3)2·3H2) and 49.30 grams of zinc nitrate (Zn (NO O3)2·6H2O) in Yu Tongyi container, add 200g Water, stirring and dissolving obtain 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 3.37 grams LiOH, 9.55CsOH grams of aqueous solution 50g is made with the pH value that concentration adjusts above-mentioned slurry for 27% (weight) ammonium hydroxide The pH=6.0 of mixed slurry, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, specific spraying Drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millimeters It is roasted 2.0 hours in the rotary roasting furnace of (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Li6Cs6La5Ox+ 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 330.60 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 11.80 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 114.80 gram of 50% manganese nitrate (Mn (NO3)2)、 29.36 grams of copper nitrate (Cu (NO3)2·3H2) and 48.69 grams of zinc nitrate (Zn (NO O3)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 3.29 grams of KOH, 9.43 grams of CsOH is that 27% (weight) ammonium hydroxide adjusts the pH value of above-mentioned slurry and makes with concentration The pH=6.0 of mixed slurry is obtained, manufactured slurry carries out framboid molding in spray dryer after being sufficiently stirred, specific to spray Mist drying condition is 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, length is 1700 millis It is roasted 2.0 hours in the rotary roasting furnace of rice (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured catalyst composition Are as follows:
50 weight %Fe100Mn40Zn20Cu15K6Cs6La5Ox+ 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 337.50 grams of ferric nitrate (Fe (NO3)3·9H2O), add 500g water to dissolve, obtain material I, take 12.00 grams of nitric acid Lanthanum (La (NO3)3·6H2O) plus 100g water dissolves by heating, and obtains material II, takes 117.20 gram of 50% manganese nitrate (Mn (NO3)2)、 29.97 grams of copper nitrate (Cu (NO3)2·3H2) and 49.70 grams of zinc nitrate (Zn (NO O3)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 2.24 grams of KOH, 2.26 grams of LiOH, 6.42 grams of CsOH is that 27% (weight) ammonium hydroxide adjusts above-mentioned slurry with concentration The pH value of material makes the pH=6.0 of mixed slurry, and manufactured slurry carries out framboid in spray dryer after being sufficiently stirred Molding, specific spray drying condition are 300 DEG C of spraying machine inlet temperature, 200 DEG C of outlet temperature.It is finally 89 millimeters in internal diameter, Length is to roast 2.0 hours in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 500 DEG C of air atmospheres, manufactured Catalyst composition are as follows:
50 weight %Fe100Mn40Zn20Cu15Li4K4Cs4La5Ox+ 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 (8)

1. the ferrum-based catalyst of one-step method from syngas producing light olefins, including carrier and active component, the active component contain With atomic ratio measuring, the following composition of chemical formula:
Fe100MnaZnbCucQfOx；
Q includes selected from least one of lanthanide series；
The value range of a is 5.0~60.0；
The value range of b is 5.0~60.0；
The value range of c is 1.0~30.0；
The value range of f is 0.9~40.0；
X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst.
2. catalyst according to claim 1, it is characterized in that carrier includes in silica, aluminium oxide and titanium oxide At least one.
3. catalyst according to claim 1, it is characterized in that the value range of a is 10.0~50.0.
4. catalyst according to claim 1, it is characterized in that the value range of b is 10.0~50.0.
5. catalyst according to claim 1, it is characterized in that the value range of c is 5.0~25.0.
6. catalyst according to claim 1, it is characterized in that the catalyst is used for one-step method from syngas producing light olefins Reaction before first pass through reduction.
7. application of the catalyst described in claim 1 in one-step method from syngas reaction for preparing light olefins.
8. the preparation method of catalyst described in claim 1, comprises the following steps that:
The slurry including catalyst carrier and active component element is obtained, the pH value of slurry is 1~6；
Slurry is sent into spray dryer spray shaping；
Roasting.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113926461A (en) * 2020-06-29 2022-01-14 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof

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Publication number Priority date Publication date Assignee Title
CN105363458A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for synthesizing light hydrocarbon and preparation method of catalyst
CN105363463A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for synthesizing gas light hydrocarbon and preparation method of catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105363458A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for synthesizing light hydrocarbon and preparation method of catalyst
CN105363463A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for synthesizing gas light hydrocarbon and preparation method of catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113926461A (en) * 2020-06-29 2022-01-14 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof
CN113926461B (en) * 2020-06-29 2024-01-12 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof

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