CN111068691B - Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof - Google Patents

Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof Download PDF

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CN111068691B
CN111068691B CN201811214379.0A CN201811214379A CN111068691B CN 111068691 B CN111068691 B CN 111068691B CN 201811214379 A CN201811214379 A CN 201811214379A CN 111068691 B CN111068691 B CN 111068691B
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catalyst
value range
slurry
carbon olefin
reduction
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CN111068691A (en
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陶跃武
庞颖聪
李剑锋
宋卫林
顾一丹
陆捷
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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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J23/89—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
    • B01J23/896—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 gallium, indium or thallium
    • 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
    • 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 invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof, which mainly solves the problem of lower selectivity of low-carbon olefin in the prior art. Fe (Fe) 100 Cu a Co b Ga c D j O x The method comprises the steps of carrying out a first treatment on the surface of the D comprises at least one selected from alkali metal and alkaline earth metal; the value range of a is 5.0-60.0; b has a value range of 1.0-20.0; c has a value range of 1.0-20.0; the value range of j is 0.01-55.0; x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst. The technical proposal of the method solves the problem well, and can be used in the industrial production of directly preparing low-carbon olefin from the fluidized bed synthesis gas.

Description

Catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof
Technical Field
The invention relates to a catalyst for directly preparing low-carbon olefin from synthesis gas and application thereof.
Background
The catalytic conversion of synthesis gas to hydrocarbons is a process of forming a mixture of linear alkanes and alkenes based on heterogeneous catalytic hydrogenation of CO over a metal catalyst, which was invented in 1923 by the german scientist Frans Fischer and Hans Tropsch, abbreviated as F-T. The germany was studied and developed in the last 20 th century, and realized industrialization in 1936, and was later shut down because of the inability to compete economically with the petroleum industry; south Africa has abundant coal resources, but the petroleum resources are poor, so the development of the coal-to-oil industry technology is continuously focused on, and a first coal-based F-T synthetic oil plant (Sasol-1) with the production capacity of 25-40 ten thousand tons of products per year is built in 1955.
The two world petroleum crisis in 1973 and 1979 caused the fluctuation of the price of crude oil in the world, and the F-T synthesis technology arouses the interest of industrialized countries again based on the consideration of strategic technical reserves. In 1980 and 1982, the Sasol company in south Africa built and put into production two coal-based synthetic oil plants one after the other. But the world price of oil drops greatly in 1986, which delays the large-scale industrialized progress of F-T synthesis technology in other countries.
In the 90 s of the twentieth century, petroleum resources are increasingly in short supply and poor quality, and coal and natural gas exploration reserves are continuously increased, so that the F-T synthesis technology is attracting attention. At present, the main raw materials of the low-carbon olefin in the world are petroleum hydrocarbons, wherein naphtha accounts for most of the petroleum hydrocarbons, and alkane, hydrogenated diesel oil, part of heavy oil and the like. Natural gas or light petroleum fractions are mostly used as raw materials at home and abroad, the low-carbon olefin is produced by adopting a steam cracking process in an ethylene combined device, steam cracking is a large energy consumption device in petrochemical industry, and is completely dependent on nonrenewable petroleum resources, so that substitute resources are required to be searched for urgently along with the gradual shortage of the petroleum resources. So research work for preparing olefin by replacing petroleum with other resources is increasingly paid attention to, and some famous petroleum companies and scientific research institutions in the world have conducted the research in this aspect and have achieved good results.
Over decades, F-T synthesis catalysts have also evolved to a significant extent, and fischer-tropsch synthesis catalysts typically comprise the following components: active metals (group VIII)Transition metal), oxide support or structure aid (SiO 2 ,Al 2 O 3 Etc.), chemical auxiliary agents (alkali metal oxides, transition metals) and noble metal auxiliary agents (Ru, re, etc.). Fe generates a large amount of olefin and oxygen-containing compounds, ru and Co mainly generate long-chain saturated hydrocarbon, and Ni mainly generates methane. Because of the serious loss of carbonyl compounds and methanation of Ni, ru and Rh are expensive, the catalysts commonly used at present are divided into two main types from the aspect of active components: iron-based catalysts and cobalt-based catalysts. The selectivity of the cocatalyst on the low-carbon olefin is greatly affected, the improvement of the selectivity of the low-carbon olefin is mainly realized through the cocatalyst, and the selection and addition technology of the cocatalyst are one of key technologies for developing an excellent catalyst.
F-T synthesis reactors are further classified into fixed bed reactors, fluidized bed reactors and slurry bed reactors according to the catalysts used and the target products. The fixed bed reactor has complex structure, high price, difficult heat removal and lower productivity of the whole device. The slurry bed has the characteristics of lower reaction temperature, easy control, lower conversion rate, most of products of high-carbon hydrocarbon and difficult liquid-solid separation of slurry in the reactor. The fluidized bed reactor has the characteristics of higher temperature, higher conversion rate, no difficulty in liquid-solid separation and most of products are low-carbon hydrocarbon; the construction and operating costs are lower, while the low pressure difference saves a lot of compression costs and is more advantageous for removing the heat evolved in the reaction, while the abrasion problems are smaller due to the low gas line speed, which makes long-term operation possible.
The iron catalyst has many advantages, such as obtaining low-carbon olefin with high selectivity, preparing gasoline with high octane number, etc., and the iron-based catalyst has the characteristics of wide operating conditions and large product adjustability. The preparation method of the iron-based catalyst mainly comprises three steps: the precipitation method (precipitation catalyst) includes such steps as proportionally mixing Mn, cu and K additives except Fe, heating to boil, adding precipitant, stirring, filtering and washing. Reslurrying the obtained filter cake with water, adding quantitative potassium silicate, drying, extruding to form, grinding and sieving; sinteringA method (sintering catalyst); oxide mixing method (iron-melting catalyst) using mill scale or magnetite powder of mill as raw material, adding adjuvant Al 2 O 3 MgO, mnO, cuO, etc., are fed into an arc furnace at 1500 ℃ for melting, and the effluent melt is molded, cooled and crushed in multiple stages.
At present, the direct F-T synthesis of low-carbon olefin by an iron-based catalyst is mostly carried out in a fixed bed, for example, an iron-based catalyst for Fischer-Tropsch synthesis of low-carbon olefin is mentioned in patent CN1040397C, and the selectivity of the low-carbon olefin can be as high as 69%. However, the fixed bed reactor has the disadvantages of complex structure, high price, difficult heat removal and lower productivity of the whole device. The fluidized bed reactor has the characteristics of higher temperature, higher conversion rate, no difficulty in liquid-solid separation and most of products are low-carbon hydrocarbon; the construction and operating costs are lower, while the low pressure difference saves a lot of compression costs and is more advantageous for removing the heat evolved in the reaction, while the abrasion problems are smaller due to the low gas line speed, which makes long-term operation possible. Most of the iron-melting catalysts used in fluidized bed F-T synthesis have been reported, for example, patent CN1704161A mentions an iron-melting catalyst used in F-T synthesis; however, the existing fluidized bed F-T synthesis has the problems of insufficient concentration of products and insufficient selectivity of low-carbon olefin.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of low selectivity of low-carbon olefin in the prior art, and provide an iron-based catalyst for directly preparing low-carbon olefin from synthesis gas, which has the characteristic of high selectivity of low-carbon olefin.
The second technical problem to be solved by the invention is the application of the catalyst.
The third technical problem to be solved by the invention is a preparation method of the catalyst.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
the catalyst for directly preparing low-carbon olefin from synthesis gas comprises a carrier and an active component, wherein the active component comprises a composition with the following chemical formula in terms of atomic ratio:
Fe 100 Cu a Co b Ga c D j O x
d includes at least one selected from alkali metals and alkaline earth metals;
the value range of a is 5.0-60.0;
b has a value range of 1.0-20.0;
c has a value range of 1.0-20.0;
the value range of j is 0.01-55.0;
x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst.
In the above technical scheme, the carrier is not particularly limited, and those commonly used in the art may be employed, for example, but not limited to, at least one of alumina, silica and titania.
In the above-mentioned technical solution, the alkali metal is preferably at least one of the group consisting of Li, na, K, rb and Cs.
In the above-mentioned technical solution, the alkaline earth metal is preferably at least one selected from the group consisting of Be, mg, ca, sr and Ba.
In the above technical scheme, D further preferably includes alkali metal, alkaline earth metal, noble metal and rare earth metal at the same time, and in this case, the active component preferably contains a composition having the following chemical formula in terms of atomic ratio:
Fe 100 Cu a Co b Ga c Na d Ca e A f L g O x
a is at least one of noble metals;
l is selected from at least one of lanthanide metals;
the value range of a is 5.0-60.0;
b has a value range of 1.0-20.0;
c has a value range of 1.0-20.0;
d has a value range of 0.1-10.0;
e has a value range of 1.0-20.0;
f has a value range of 0.01 to 0.5;
the value range of g is 0.1-10.0;
x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst.
In the above technical solution, the noble metal is preferably at least one of the group consisting of Pd, pt, ru and Rh; more preferably, the noble metal comprises at least two of Pd, pt and Ru simultaneously, and in this case, for example, pd and Pt, pd and Ru, pt and Ru have a synergistic effect in improving the selectivity of the low-carbon olefin. The atomic ratio between the two elements at this time is not particularly limited, for example, but not limited to, 0.1 to 10, wherein more specific atomic ratios may 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, 6.0, 7.0, 8.0, 9.0, and the like.
In the technical scheme, the value 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 the above technical solution, the value of b is preferably in the range of 5.0-45.0, such as but not limited to 15.0, 20.0, 25.0, 30.0, 35.0, 40.0, 45.0, etc.
In the above technical solution, the value of c is preferably in the range of 5.0-15.0, such as but not limited to 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, etc.
In the above technical solution, the value of d is preferably in the range of 1.0-8.0, such as but not limited to 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, etc.
In the above technical solution, the value of e is preferably in the range of 5.0-15.0, such as but not limited to 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, etc. .
In the above technical solution, the value of f is preferably in the range of 0.01 to 0.4, for example, but not limited to, 0.05, 0.1, 0.15, 0.2, 0.25, 0.30, 0.35, etc.
In the above technical solution, the value of g is preferably in the range of 5.0-15.0, such as but not limited to 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, etc.
In the above technical solution, the lanthanoid element includes Ce.
In the above technical solution, the amount of the carrier is not particularly limited, and may be reasonably selected by those skilled in the art without any inventive effort. Such as, but not limited to, the amount of support is in the range of 20 to 80% by weight of the catalyst, and within this range, as point of use values, for example, without limitation, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, etc., more preferably 30 to 70%.
The catalyst of the invention can be reduced or not before being used for the reaction of producing the low-carbon olefin by the synthesis gas one-step method, but is preferably reduced. When reducing, the reducing conditions are not particularly limited and may be reasonably selected by those skilled in the art, such as, but not limited to, the reducing conditions of the catalyst prepared according to the present invention: the pressure is 0.05-5 MPa, preferably 0.1-4 MPa; the reducing gas may be hydrogen, carbon monoxide or synthesis gas, and when synthesis gas is used, H 2 The molar ratio of CO is 0.1-6.0, preferably 0.2-6.0; the load of the reducing gas is 100-8000 mL.h -1 ·g -1 Preferably 500 to 6000 mL.h -1 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The reduction temperature is 200-600 ℃, preferably 220-500 ℃; the reduction time is 1 to 100 hours, preferably 6 to 72 hours.
For comparison, the reduction conditions used for the catalysts prepared in the embodiments of the present invention are:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas (molar ratio) H 2 /CO＝2/1
The reduction time was 24 hours.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the application of the catalyst in the preparation of low-carbon olefin by directly synthesizing gas.
The technical key of the invention is the choice of catalyst, which can be reasonably selected by the person skilled in the art for the specific application of process conditions without the need for inventive effort, such as but not limited to:
in the presence of the catalyst in any one of the technical schemes, the synthesis gas reacts to generate the low-carbon olefin.
Those skilled in the art will appreciate that lower olefins refer to C2 to C4 olefins, more specifically ethylene, propylene and butylene or mixtures thereof. The butene comprises butene-1, butene-2, isobutene and butadiene.
The reaction temperature can be 200-600 ℃, preferably 220-500 ℃;
the pressure of the reaction may be 0.5 to 10MPa, preferably 1 to 8MPa; the method comprises the steps of carrying out a first treatment on the surface of the
H in synthesis gas 2 The molar ratio of/CO may be from 0.1 to 5.0, preferably from 0.5 to 3.0;
the volume space velocity of the synthesis gas can be 100-8000 mL.h based on the amount of the catalyst before reduction -1 ·g -1 Preferably 500 to 6000 mL.h -1 ·g -1 More preferably 2000 to 6000 mL.multidot.h -1 ·g -1 。
For comparison, the evaluation conditions of the catalysts used in the embodiments of the present invention were:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
In order to solve the third technical problem of the invention, the technical scheme of the invention is as follows:
the preparation method of the catalyst according to any one of the technical schemes comprises the following process steps:
obtaining slurry comprising a catalyst carrier and active component elements, wherein the pH value of the slurry is 1-6;
feeding the slurry into a spray dryer for spray forming;
and (5) roasting.
When the active component contains both the lanthanide and the alkali metal element, the catalyst is preferably prepared by a process comprising the following steps:
obtaining an aqueous solution comprising a metal element other than an alkali metal in the composition;
adding the needed amount of carrier sol into the aqueous solution, adding alkali metal hydroxide solution, and regulating the pH value to 1-6 by using an acid-base regulator to obtain slurry;
feeding the slurry into a spray dryer for spray forming;
and (5) roasting.
In the above technical scheme, the roasting temperature is preferably 400-1000 ℃, more preferably 450-800 ℃.
In the above-mentioned embodiments, the baking time is preferably 0.15 to 10 hours, more preferably 0.5 to 8 hours.
The process conditions for spray drying molding are not particularly limited, and can be reasonably selected by those skilled in the art and can achieve comparable technical effects. For example, but not limited to, the spray can be formed into microspheres by spray drying under the condition that the inlet temperature of the spray can be 200-380 ℃ and the outlet temperature can be 100-230 ℃, and finally the catalyst is prepared by roasting.
For convenience of comparison, the spray drying conditions adopted in the specific embodiment of the invention are as follows:
the inlet temperature is 300 ℃,
the outlet temperature was 200 ℃.
In the above technical scheme, the soluble ferric salt may be ferric nitrate or ferric sulfate.
In the above technical solution, the soluble compounds of Cu, co, ga, mg, ca and lanthanoid may be nitrate or salts which can be decomposed into oxides.
In the above technical scheme, the soluble compound of Na may be nitrate, chloride or hydroxide.
In the above technical solution, the soluble compound of the noble metal may be nitrate, chloride or complex acid of the noble metal.
In the above-mentioned embodiments, the baking atmosphere is not particularly limited, but is preferably an oxidizing atmosphere or an inert atmosphere, and is more preferably an air atmosphere for economic reasons.
In the present invention, unless otherwise indicated, the pressure including the reaction pressure means the gauge pressure.
The catalyst of the present invention is used in the reaction at 200-600 deg.c and 0.5-10 MPa and with catalyst load of 100-8000 ml.h -1 ·g -1 Raw material ratio (mol) H 2 And the F-T synthesis reaction is carried out under the condition of (0.1-5.0): 1, the CO conversion rate can reach 91.5%, the selectivity of the low-carbon olefin in the reaction product can reach 71.2%, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Catalyst preparation
416.0 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.30 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.56 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.13 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.30 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Mixing materials I, II and III, adding 312.5 g of 40% (weight) aluminum sol material under stirring, adding 50g of solution containing 1.60 g of NaOH, adjusting the pH value of the slurry with ammonia water to ensure that the pH value of the mixed slurry is=6.0, forming microspheres in a spray dryer according to a conventional method after fully stirring, and finally roasting the prepared slurry in a rotary roasting furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 multiplied by 1700 mm) at 500 ℃ for 2.0 hours, wherein the prepared catalyst comprises the following components:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 2 ]
1. Catalyst preparation
415.2 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.30 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.44 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.10 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.20 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Mixing materials I, II and III, adding 312.5 g of 40% by weight aluminum sol material under stirring, and then adding 50g of solution containing 1.60 g of NaOH and 0.60 g of PdCl 2 The pH of the slurry was adjusted with aqueous ammonia so that the ph=6.0 of the mixed slurry, and the resulting slurry was subjected to microsphere formation in a spray dryer by a usual method after sufficient stirring, and finally calcined in a rotary kiln having an inner diameter of 89 mm and a length of 1700 mm (Φ89×1700 mm) at 500 ℃ for 2.0 hours, to give a catalyst composition comprising:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pd 0.2 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 3 ]
1. Catalyst preparation
414.5 g of nitreIron (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.20 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.34 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.08 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.20 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.60 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed and 312.5 g of 40% by weight aluminum sol material was added with stirring, followed by 50g of a solution containing 1.60 g of NaOH and 2.78 g of H 2 PtCl 6 ·6H 2 50g of O solution, adjusting the pH value of the slurry by ammonia water to ensure that the pH value of the mixed slurry is=6.0, forming microspheres in a spray dryer by a conventional method after fully stirring the prepared slurry, and finally roasting the prepared slurry in a rotary roasting furnace with the inner diameter of 89 mm and the length of 1700 mm (phi 89 multiplied by 1700 mm) at 500 ℃ for 2.0 hours to prepare a catalyst with the following composition:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pt 0.2 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 4 ]
1. Catalyst preparation
415.1 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.20 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.43 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.10 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.20 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Mixing materials I, II and III, adding 312.5 g of 40% by weight aluminum sol material under stirring, and then adding 50g of solution containing 1.60 g of NaOH and 0.85 g of RuCl 3 The acidity of the slurry was adjusted with ammonia so that the ph=6.0 of the mixed slurry, the slurry was obtained after sufficient stirring, the prepared slurry was subjected to microsphere formation in a spray dryer, and finally the catalyst composition was calcined:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Ru 0.2 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 5 ]
1. Catalyst preparation
414.8 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.20 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.39 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.09 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.20 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed and 312.5 g of 40% by weight aluminum sol material was added with stirring, followed by 50g of a solution containing 1.60 g of NaOH and 0.30 g of PdCl 2 Containing 1.39 g of H 2 PtCl 6 ·6H 2 50g of O solution, regulating the acidity of the slurry by ammonia water to ensure that the pH value of the mixed slurry is=6.0, fully stirring to obtain the slurry, forming microspheres in a spray dryer, and finally roasting the prepared catalyst groupThe method comprises the following steps:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pd 0.1 Pt 0.1 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 6 ]
1. Catalyst preparation
415.1 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.30 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.43 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.10 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.20 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed and 312.5 g of 40% by weight aluminum sol material was added with stirring, followed by 50g of a solution containing 1.60 g of NaOH and 0.30 g of PdCl 2 Containing 0.43 g RuCl 3 The acidity of the slurry was adjusted with ammonia so that the ph=6.0 of the mixed slurry, the slurry was obtained after sufficient stirring, the prepared slurry was subjected to microsphere formation in a spray dryer, and finally the catalyst composition was calcined:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pd 0.1 Ru 0.1 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 7 ]
1. Catalyst preparation
414.8 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 800g of water to give a material I, 13.20 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 61.38 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 15.09 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 19.20 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 23.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed and 312.5 g of 40% by weight aluminum sol material was added with stirring, followed by 50g of a solution containing 1.60 g of NaOH and 1.39 g of H 2 PtCl 6 ·6H 2 O, containing 043 g RuCl 3 The acidity of the slurry was adjusted with ammonia so that the ph=6.0 of the mixed slurry, the slurry was obtained after sufficient stirring, the prepared slurry was subjected to microsphere formation in a spray dryer, and finally the catalyst composition was calcined:
50 wt% Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pt 0.1 Ru 0.1 O x +50 wt% Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 8 ]
1. Catalyst preparation
562.0 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 1000g of water to give a material I, 47.80 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 200g of water to obtain a material II, 33.27 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 12.78 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 48.80 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 60.10 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed and 187.5 g of 40% by weight aluminum sol material were added with stirring, followed by 50g of a solution containing 4.40 g of NaOH and 1.62 g of PdCl 2 0.58 g RuCl 3 The acidity of the slurry is adjusted by ammonia water to ensure that the pH=6.0 of the mixed slurry, the slurry is obtained after full stirring, the prepared slurry is subjected to microsphere forming in a spray dryer, and finally the catalyst prepared by roasting comprises the following components:
70 wt% Fe 100 Cu 10.0 Co 15.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 8.0 Ru 0.1 Pd 0.4 O x +30% by weight of Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
[ example 9 ]
1. Catalyst preparation
216.5 g of ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O) was dissolved in 600g of water to give a material I, 2.30 g of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) was dissolved by heating with 50g of water to obtain a material II, 64.04 g of copper nitrate (Cu (NO) 3 ) 2 ·3H 2 O), 14.75 g of gallium nitrate (Ga (NO) 3 ) 3 ·9H 2 O), 6.30 g of calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O), and 7.70 g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) adding 500g of water into the same container, stirring and dissolving to obtain a material III.
Materials I, II and III were mixed and 187.5 g of 40% by weight aluminum sol material were added with stirring, followed by 50g of a solution containing 0.20 g of NaOH and 0.16 g of PdCl 2 0.89 g RuCl 3 The acidity of the slurry is adjusted by ammonia water to ensure that the pH=6.0 of the mixed slurry, the slurry is obtained after full stirring, the prepared slurry is subjected to microsphere forming in a spray dryer, and finally the catalyst prepared by roasting comprises the following components:
30 wt% Fe 100 Cu 50.0 Co 5.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 1.0 Ru 0.4 Pd 0.01 O x +70% by weight of Al 2 O 3
2. Reduction and evaluation of catalysts
The catalyst prepared is subjected to reduction conditions:
at a temperature of 400 DEG C
Pressure 3.0MPa
Catalyst loading 100g
Catalyst loading 4000 mL.h -1 ·g -1
Reducing gas H 2 /CO＝2/1
Reduction time 24 hours
The reduction is carried out and then the Fischer-Tropsch reaction is carried out under the following conditions:
phi 38 mm fluidized bed reactor
The reaction temperature is 330 DEG C
The reaction pressure was 2.0MPa
The catalyst loading corresponds to 100g of the catalyst before reduction
Catalyst loading was 3000 mL.h based on the amount of catalyst before reduction -1 ·g -1
Raw material ratio (mol) H 2 /CO＝2/1。
The experimental results of the synthesis reaction are shown in Table 1.
Table 1 (waiting)
Active ingredient/wt% Carrier/wt%
Example 1 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 O x 50% by weight Al 2 O 3 50% by weight
Example 2 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pd 0.2 O x 50% by weight Al 2 O 3 50% by weight
Example 3 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pt 0.2 O x 50% by weight Al 2 O 3 50% by weight
Example 4 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Ru 0.2 O x 50% by weight Al 2 O 3 50% by weight
Example 5 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pd 0.1 Pt 0.1 O x 50% by weight Al 2 O 3 50% by weight
Example 6 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pd 0.1 Ru 0.1 O x 50% by weight Al 2 O 3 50% by weight
Example 7 Fe 100 Cu 25.0 Co 8.0 Ga 8.0 Na 4.0 Ca 8.0 Ce 3.0 Pt 0.1 Ru 0.1 O x 50% by weight Al 2 O 3 50% by weight
Example 8 Fe 100 Cu 10.0 Co 15.0 Ga 5.0 Na 8.0 Ca 15.0 Ce 8.0 Ru 0.1 Pd 0.4 O x 70 wt.% Al 2 O 3 30 wt%
Example 9 Fe 100 Cu 50.0 Co 5.0 Ga 15.0 Na 1.0 Ca 5.0 Ce 1.0 Ru 0.4 Pd 0.1 O x 30 wt% Al 2 O 3 70 wt.%
Table 1 (subsequent)
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Claims (8)

1. The catalyst for directly preparing low-carbon olefin from synthesis gas comprises a carrier and an active component, wherein the active component comprises a composition with the following chemical formula in terms of atomic ratio:
Fe 100 Cu a Co b Ga c Na d Ca e A f L g O x
a comprises Pd and Pt or Pt and Ru at the same time;
l is Ce;
the value range of a is 5.0-60.0;
b has a value range of 1.0-20.0;
c has a value range of 1.0-20.0;
d has a value range of 0.1-10.0;
e has a value range of 1.0-20.0;
f has a value range of 0.01 to 0.5;
the value range of g is 0.1-10.0;
x is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst.
2. The catalyst of claim 1, wherein the support comprises at least one of silica, alumina, and titania.
3. The catalyst of claim 1, wherein a has a value in the range of 10.0 to 50.0.
4. The catalyst of claim 1, wherein b has a value in the range of 5.0 to 15.0.
5. The catalyst according to claim 1, wherein the carrier is used in an amount of 20 to 80% by weight of the catalyst.
6. The catalyst according to claim 1, wherein the catalyst is reduced prior to the reaction for directly producing low-carbon olefin from synthesis gas.
7. Use of the catalyst according to any one of claims 1 to 6 in the direct production of light olefins from synthesis gas.
8. A process for the preparation of a catalyst as claimed in claim 1, comprising the following process steps:
obtaining slurry comprising a catalyst carrier and active component elements, wherein the pH value of the slurry is 1-6;
feeding the slurry into a spray dryer for spray forming;
and (5) roasting.
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CN101811047A (en) * 2009-02-20 2010-08-25 中科合成油技术有限公司 Iron base catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof
CN103331171A (en) * 2013-07-08 2013-10-02 华东理工大学 Preparation method and applications of catalyst used for preparing light olefin from synthesis gas
CN103464169A (en) * 2012-06-07 2013-12-25 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst, preparation and application thereof
CN104549296A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof
CN105363464A (en) * 2014-08-27 2016-03-02 中国石油化工股份有限公司 Catalyst for directly preparing light hydrocarbon through synthesis gas and preparation method of catalyst
CN106000404A (en) * 2016-05-24 2016-10-12 江南大学 Preparation and application of carbon modified silicon dioxide carrier loaded iron-based catalyst for Fischer-Tropsch synthesis

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CN101811047A (en) * 2009-02-20 2010-08-25 中科合成油技术有限公司 Iron base catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof
CN103464169A (en) * 2012-06-07 2013-12-25 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst, preparation and application thereof
CN103331171A (en) * 2013-07-08 2013-10-02 华东理工大学 Preparation method and applications of catalyst used for preparing light olefin from synthesis gas
CN104549296A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for directly preparing low-carbon olefin from microspherical synthesis gas, as well as preparation method thereof
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