CN109382082A - Carrier and preparation method thereof and fischer-tropsch synthetic catalyst and Fischer-Tropsch synthesis method - Google Patents
Carrier and preparation method thereof and fischer-tropsch synthetic catalyst and Fischer-Tropsch synthesis method Download PDFInfo
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- CN109382082A CN109382082A CN201710692812.0A CN201710692812A CN109382082A CN 109382082 A CN109382082 A CN 109382082A CN 201710692812 A CN201710692812 A CN 201710692812A CN 109382082 A CN109382082 A CN 109382082A
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to field of catalyst preparation, disclose a kind of carrier and preparation method thereof and fischer-tropsch synthetic catalyst and Fischer-Tropsch synthesis method, the preparation method of carrier includes: by support precursor extruded moulding, obtain molding, molding is subjected to steam treatment in steam-laden atmosphere, obtain carrier, the type of the mode of the extruded moulding, the condition of steam treatment and support precursor, so that the average pore diameter of carrier obtained increases compared with the average pore diameter of support precursor, it is characterized by BET nitrogen absorption under low temperature, increase △ n is at least
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a carrier and a preparation method thereof, and a Fischer-Tropsch synthesis catalyst and a Fischer-Tropsch synthesis method.
Background
Good Fischer-Tropsch synthesis catalyst, which is used for treating CO and H2Has adsorption activity, and has hydrogenation effect on the adsorbed CO, and simultaneously, the hydrogenation effect is not too strong, the water gas shift is too much, and the formation of inactive carbide and the like are avoided. The first step in Fischer-Tropsch Synthesis is CO and H2The transition elements having 3d and 4f bonds and energy levels are mostly used as active components of the fischer-tropsch synthesis catalyst from the structural chemistry point of view. Among them, studies on Ni, Fe, Co and Ru have been made.
The influence of the carrier on the cobalt-based catalyst in the Fischer-Tropsch synthesis process is complex, and foreign companies have various characteristics on the selection of the catalyst carrier and the preparation of the catalyst. SiO 22The surface area is high, the carrier is commonly used, and the research and development of Shell company are mainly internationally conducted and industrialized. Al (Al)2O3The wear resistance of the alloy is good, the mechanical strength is high, the alloy is suitable for slurry bed operation, and the research and development of Sasol, Gulf/Chevron and Statoil companies are taken as main international points. TiO 22Other oxides (e.g. SiO) are often required as supports2、Al2O3And ZrO2) The modification is mainly developed by ExxonMobil internationally.
The effect of the support on the performance of cobalt-based catalysts is multifaceted, with Anderson et al believing that the reactant molecule H2And the diffusion rate of CO in the catalyst channels filled with liquid phase product (H)2Faster than CO),make the hole channel with smaller hole channel interior H2higher/CO, the synthesized hydrocarbon product distribution must be biased towards lower hydrocarbons, with a corresponding decrease in chain growth factor. Saib et al investigated the pore size of silica gel on Co/SiO2The structure of the catalyst and the influence of the Fischer-Tropsch synthesis performance show that: the pore size affects the cobalt species crystallite size, cobalt reduction and cobalt dispersion, and when the pore size is about 10 nm, the catalyst has the highest reactivity, the lowest methane content in the hydrocarbon distribution, and C5+The hydrocarbon content is highest. Studies on silica gels with different pore diameters such as Chenjianggang show that the conversion rate of CO does not change much with the increase of the pore diameter, but C5+The selectivity of the hydrocarbon increases and the probability of chain growth increases. From the above, it can be seen that the performance of the fischer-tropsch synthesis reaction can be improved by selecting a catalyst prepared with a support having an appropriate pore size.
CN1190267C discloses a catalyst for preparing mainly diesel fraction hydrocarbon from synthesis gas, which consists of active components, auxiliary agents and a carrier. The main active component is metallic cobalt, the first auxiliary agent element is from IVB group metal elements, such as Ti, Zr or IIIB group metal elements, such as La, Ce and the like, and the second auxiliary agent element is from VIII group metal elements, such as Rh, Ru, Pt and the like. The carrier is apricot kernel active carbon, coconut shell active carbon, oil palm active carbon or coal-made active carbon, and the specific surface area of the active carbon is 200-2000m2Per g, pore volume of 0.5-2.0cm3(ii) a pore size distribution of 4 to 1000 angstroms per gram. The metal cobalt accounts for 4-50% (weight) of the total weight of the catalyst, the first auxiliary agent element accounts for 0.0-20.0% of the total weight of the catalyst, and the second auxiliary agent element accounts for 0.01-5.0%. The catalyst can be used for directly preparing high-quality clean liquid fuels such as diesel oil and the like from synthesis gas through Fischer-Tropsch synthesis reaction. Although the activity of the catalyst is improved to some extent, the activity, selectivity and stability of the Fischer-Tropsch synthesis catalyst are still required to be further improved.
Therefore, there is a need to develop a new method for preparing a carrier, and further to obtain a fischer-tropsch synthesis catalyst with more excellent performance.
Disclosure of Invention
The invention aims to overcome the defect that the Fischer-Tropsch synthesis catalyst in the prior art is difficult to have high C5+The defects of hydrocarbon selectivity, high stability, high CO conversion rate, low carbon dioxide and methane selectivity, and provides a preparation method of a carrier, the carrier prepared by the method, a Fischer-Tropsch synthesis catalyst and a Fischer-Tropsch synthesis method. The pore diameter of the carrier prepared by the preparation method of the carrier provided by the invention is increased, the preparation process is simple, the energy consumption is low, and the Fischer-Tropsch synthesis catalyst prepared by the carrier provided by the invention has better activity, selectivity and stability.
In the research process, the inventor of the invention finds that the carrier has great influence on the grain size of the cobalt-based catalyst metal and the interaction between cobalt and the carrier, and the organizational structure and the surface acid-base property of the carrier also influence the performance of the cobalt-based catalyst, and finally influence the Fischer-Tropsch synthesis reaction performance of the catalyst. In the conventional process for preparing a catalyst carrier, in order to obtain a carrier having a larger pore diameter, it is generally carried out by adding a pore-expanding agent, hydrothermal treatment or high-temperature calcination. However, each of these methods has some drawbacks, and in particular, although the addition of pore-expanding agents adds some macropores to the catalyst support, the inherent small pores are still not removed; the hydrothermal treatment method or the high-temperature roasting method has the defects of large energy consumption and long period, and for the carrier containing the molecular sieve, the molecular sieve collapse can be caused by the high-temperature roasting, so that the performance of the catalyst is influenced. In contrast, the inventors of the present invention have found, in further studies, that, in the preparation of a fischer-tropsch synthesis catalyst, the average pore diameter of a carrier can be significantly increased under mild conditions by subjecting a molded product obtained by extrusion molding to steam treatment, and that a catalyst prepared from the carrier can improve the performance of a fischer-tropsch synthesis reaction.
Based on this, the present invention provides a method for preparing a carrier, the method comprising:
extruding the carrier precursor to form a strip, obtaining a formed object, and carrying out steam vapor treatment on the formed object in an atmosphere containing steamTreating to obtain a carrier, wherein the extrusion molding mode, the water vapor treatment condition and the type of the carrier precursor are such that the average pore diameter of the prepared carrier is larger than that of the carrier precursor, and the increase amount △ n is at least equal to the BET low-temperature nitrogen adsorption representation△ n is n2-n1, n1 is the average pore diameter of the carrier precursor, and n2 is the average pore diameter of the prepared carrier.
According to a preferred embodiment of the present invention, the carrier precursor is mixed with the surfactant, and then the extrusion molding is performed, and the carrier obtained by using this preferred embodiment undergoes the dual actions of the surfactant and the water vapor treatment, so that the average pore diameter of the obtained carrier is further increased.
The invention provides a carrier prepared by the preparation method.
The invention also provides a Fischer-Tropsch synthesis catalyst, which comprises a carrier and an active metal component Co loaded on the carrier, wherein the carrier is the carrier.
The invention also provides a Fischer-Tropsch synthesis method, which comprises the step of contacting the synthesis gas with the catalyst under the Fischer-Tropsch synthesis reaction condition, wherein the catalyst is the Fischer-Tropsch synthesis catalyst provided by the invention.
The preparation method of the carrier provided by the invention is simple and feasible, the conditions are mild, the prepared carrier has better physicochemical parameters, and when the catalyst prepared by adopting the carrier provided by the invention is applied to Fischer-Tropsch synthesis reaction, the catalyst has excellent performance, high activity, selectivity and stability.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a method for preparing a carrier, the method comprising:
extruding a carrier precursor to form strips, obtaining a formed object, carrying out steam treatment on the formed object in an atmosphere containing steam to obtain a carrier, wherein the average pore diameter of the prepared carrier is increased compared with that of the carrier precursor by the strip extrusion forming mode, the steam treatment condition and the type of the carrier precursor, and the increase △ n is at least represented by BET low-temperature nitrogen adsorption△ n is n2-n1, n1 is the average pore diameter of the carrier precursor, and n2 is the average pore diameter of the prepared carrier.
According to a preferred embodiment of the present invention, the increase △ n isPreferably, it isThe optimized increased amount △ n is more beneficial to improving the performance of the carrier, and the catalyst obtained by the carrier prepared by the optimized method is more beneficial to improving the activity, selectivity and stability of the catalyst when being applied to the Fischer-Tropsch synthesis process.
In the present invention, the average pore diameter of the carrier is increased from the average pore diameter of the carrier precursor by at least △ n(preferably, it isFurther preferred is) The carrier precursor is not limited in the present invention, and for example, the carrier precursor is at least one selected from precursors of alumina, silica-alumina, aluminum silicate, titania, zirconia, and molecular sieves. In the present invention, the source of the carrier precursor is not particularly limited, and may be a commercially available product or may be prepared by any conventional method. The carrier precursor may be in the form of a strip, a sphere, a powder, a sol, or a gel.
According to the present invention, preferably, the carrier precursor is an alumina precursor, and further preferably, the carrier precursor is pseudo-boehmite. In a preferred embodiment, the pseudoboehmite has an average pore diameter ofFurther preferably, the pseudoboehmite does not contain a sulfur-containing compound.
It should be noted that the term "free" as used herein does not mean absolutely free, but means substantially free. When the pseudoboehmite contains a trace amount (less than 0.01 wt%) of sulfur-containing compounds, it is also understood that no sulfur-containing compounds are contained.
The carrier precursor may be a commercially available product or may be prepared by any conventional method as long as the above conditions are satisfied, and the present invention is not particularly limited thereto. For example, SB pseudo-boehmite supplied by the Sasol manufacturer.
According to a preferred embodiment of the present invention, the manner of extruding the carrier precursor includes: mixing the carrier precursor, water, extrusion aid and peptizing agent, and extruding the obtained mixed material into strips in a strip extruding machine for forming.
According to a preferred embodiment of the present invention, the method further comprises mixing the carrier precursor, water, the extrusion aid and the peptizing agent, kneading the obtained mixed material, and then performing the extrusion molding. The kneading may be performed on a kneader.
According to a preferred embodiment of the present invention, the weight ratio of water to carrier precursor in the mixed material is 0.5-1.8:1, preferably 0.55-1.5:1, and more preferably 0.68-0.75: 1; the extrusion aid is used in an amount of 0.1 to 6 parts by weight, preferably 2 to 4 parts by weight, relative to 100 parts by weight of the carrier precursor; the amount of the peptizing agent is 0.1 to 6 parts by weight, preferably 0.6 to 4 parts by weight, and more preferably 1.1 to 2.8 parts by weight.
The inventor of the invention finds that the dosage of water, the extrusion assisting agent and the peptizing agent can influence the physical and chemical parameters of the prepared carrier, and further influence the performance of the catalyst prepared by the carrier. For example, if the amount of water used is too small, the smooth progress of extrusion molding is impaired, and burrs are formed on the surface of the resulting molded article, whereas if the amount of water used is too large, the strength of the catalyst obtained thereafter is poor. The amount of peptizing agent also has an effect on the average pore diameter of the support.
It should be noted that the water, the extrusion aid and the peptizing agent do not act independently, but affect the physical and chemical properties of the carrier together.
According to the method of the present invention, the extrusion aid may be at least one selected from sesbania powder, starch and derivatives thereof, cellulose and derivatives thereof, ethylene glycol, diethylene glycol, acrylic resin, polyurethane, epoxy resin, and polyvinyl alcohol. Preferably, the extrusion aid is selected from one or more of starch and derivatives thereof, cellulose and derivatives thereof, ethylene glycol and diethylene glycol, and further preferably, the extrusion aid is selected from one or more of starch and derivatives thereof, and cellulose and derivatives thereof. The derivative of the starch can be one or more of oxidized starch, esterified starch, carboxymethyl starch, cationic starch, hydroxyalkyl starch and multi-component starch; the derivative of cellulose may be one or more of cellulose ether, cellulose ester and cellulose ether ester.
According to the method of the present invention, the peptizing agent may be selected from at least one of inorganic acids, organic acids, and strong and weak base salts, and preferably, the peptizing agent is selected from at least one of nitric acid, hydrochloric acid, acetic acid, citric acid, and aluminum nitrate.
According to the method of the present invention, the specific manner of mixing the carrier precursor, water, the extrusion aid and the peptizing agent to obtain the mixed material is not particularly limited as long as the carrier precursor, the water, the extrusion aid and the peptizing agent are mixed. Preferably, the specific manner of mixing the carrier precursor, the water, the extrusion aid and the peptizing agent comprises: mixing the carrier precursor and the extrusion aid, mixing the peptizing agent and water, and then mixing the two.
The extrusion molding mode can be a conventional mode in the field, for example, the extrusion molding mode can adopt a screw rod extrusion molding machine to extrude the strip, and can also adopt a piston type extrusion molding machine to extrude the strip.
Preferably, the plodder is a screw-type plodder. The screw rod extruder may be any one of various screw rod extruders conventionally used in the art, and the present invention is not particularly limited thereto.
According to a preferred embodiment of the invention, the method further comprises: drying the molded article, and then performing the water vapor treatment in an atmosphere containing water vapor.
According to a preferred embodiment of the invention, the drying is a flash drying. The flash drying means that the molded product reaches the target drying temperature in as short a time as possible, and the curing time is reduced because the physical properties of the carrier are lost due to the long curing time, and therefore, according to the method of the present invention, preferably, the drying includes drying the molded product within 0 to 10 hours, more preferably within 0 to 5 hours, and still more preferably within 0 to 1 hour after the extrusion. In the prior art, for better molding, in some cases, in order to meet the requirement of granulation, the extruded molded object needs to be dried after being placed for a period of time (generally more than 6 hours), and the inventors of the present invention found that drying the molded object in the period of time is more beneficial to the performance of the catalyst in the fischer-tropsch synthesis reaction process.
The present invention has a wide range of drying conditions, for example, the drying conditions may include: the temperature is 80-300 ℃, and the time is 0.5-12 hours; preferably, the temperature is 120-260 ℃ and the time is 0.7-5 hours; further preferably, the temperature is 140-.
According to a preferred embodiment of the invention, the method further comprises: and mixing the carrier precursor with a surfactant, and then carrying out extrusion molding. The inventor of the invention finds that the carrier precursor is mixed with the surfactant in the research process, and then the extrusion molding and the water vapor treatment are sequentially carried out, so that the carrier with better physical property parameters can be provided more favorably.
According to a preferred embodiment of the present invention, the manner of extruding the carrier precursor includes: mixing the carrier precursor, the surfactant, the water, the extrusion aid and the peptizing agent to obtain a material C, and extruding the material C in a strip extruder to form strips.
The weight ratio of the water to the carrier precursor in the material C, the dosage of the extrusion aid and the peptizing agent are selected within the same dosage selection range as those in the mixed material, and are not described again.
In the present invention, the amount of the surfactant is selected from a wide range, and for example, the amount of the surfactant may be 1 to 10 parts by weight, preferably 1 to 5 parts by weight, relative to 100 parts by weight of the carrier precursor.
The present invention has a wide range of selection of the kind of the surfactant, and for example, the surfactant may be at least one selected from the group consisting of a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a high molecular substance having surfactant properties.
The cationic surfactant is not particularly limited in the present invention, and may include at least one of an amine salt type cationic surfactant, a quaternary ammonium salt type cationic surfactant, and a heterocyclic type cationic surfactant, for example. The amine salt type cationic surfactant may be selected from amine salts of higher fats, ethanolamine, and polyethylene polyamine. The quaternary ammonium salt type cationic surfactant includes alkyltrimethylammonium salt type, dialkyldimethylammonium salt type, alkyldimethylbenzylammonium salt type, pyridinium salt type, alkylisoquinolinium salt type, and benzalkonium chloride salt type, and the present invention is not particularly limited thereto. The heterocyclic ring contained in the heterocyclic cationic surfactant may be at least one of a morpholine ring, a pyridine ring, an imidazole ring, a piperazine ring and a quinoline ring containing nitrogen. According to a preferred embodiment of the present invention, the cationic surfactant is preferably at least one of cocamidopropyl dimethylamine lactate, stearamidopropyl dimethylamine lactate, cetyl trimethyl ammonium chloride, tallow trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, oleyl dimethyl benzyl ammonium chloride, lauryl dimethyl amine oxide, cetyl dimethyl amine oxide and coco dihydroxyethyl amine oxide.
In the present invention, the amphoteric surfactant refers to a surfactant having both anionic and cationic ionic properties, and the present invention has a wide selection range of specific types of the amphoteric surfactant, and preferably, the amphoteric surfactant includes one or more of amino acid type surfactants and betaine type surfactants, and more preferably, one or more of cocobetaine, oleylbetaine, tallow dihydroxyethyl betaine, cocoamidopropyl betaine, and sodium hydroxymethyl glycinate.
The nonionic surfactant is a surfactant which does not generate ions in an aqueous solution, and the specific kind of the nonionic surfactant is widely selected in the present invention, and preferably, the nonionic surfactant includes a polyoxyethylene-based hydrophilic group-containing compound and a polyol-based hydrophilic group-containing compoundPreferably an alkyl polyoxyethylene ether (formula R-O (CH))2CH2O)nH, R is C9-C17 alkyl, n is an integer of 2-18), oleyl alcohol polyoxyethylene ether, stearylamine polyoxyethylene ether, castor oil polyoxyethylene ether, methyl glucoside polyoxyethylene ether and methyl glucoside polyoxypropylene ether.
The invention has wide selection range of the polymer with the surfactant property, and preferably, the polymer with the surfactant property is selected from one or more of stearic acid, polyacrylamide, polyvinyl alcohol and polyethylene glycol.
In order to further increase the average pore diameter of the carrier and optimize the physical parameters of the carrier, it is preferred that the surfactant is polyethylene glycol (PEG) and/or polyvinylpyrrolidone (PVP).
In the research process, the inventor of the invention finds that the surfactant is firstly mixed with water and/or alcohol and then mixed with the carrier precursor, the extrusion aid, the peptizing agent and optional water, so that the dispersion of the surfactant is more facilitated, and the prepared carrier has better physical property parameters. Preferably, the carrier precursor, the surfactant, the water, the extrusion aid and the peptizing agent are mixed in a manner comprising: mixing the carrier precursor, the extrusion aid, the peptizing agent and optional water to obtain a material A, mixing the surfactant with water and/or alcohol to obtain a material B, and mixing the material A and the material B to obtain a material C.
According to the invention, the specific implementation of obtaining the material a can be as follows: mixing the carrier precursor and the extrusion aid, mixing the peptizing agent and water, and then mixing the two.
The surfactant can be mixed with water to obtain a material B, can also be mixed with alcohol to obtain the material B, and can also be simultaneously mixed with water and alcohol to obtain the material B. When the surfactant is mixed with water or water and alcohol to obtain material B, the addition amount of water is less than the requirement of material C for water. When the surfactant is mixed with alcohol to obtain a material B, water needs to be added when preparing the material A, and the addition amount of the obtained water meets the requirement of the material C on the amount of the water.
The alcohol of the present invention may be an alcohol having a carbon number of 5 or less, and may be one or more of a monohydric alcohol, a dihydric alcohol and a polyhydric alcohol (an alcohol having three or more hydroxyl groups in the molecule). The alcohol is preferably selected from one or more of methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerol, pentaerythritol and xylitol.
According to the present invention, preferably, the carrier precursor, the surfactant, the water, the extrusion aid, and the peptizing agent are mixed in a manner including: mixing the carrier precursor, the extrusion aid, the peptizing agent and water to obtain a material A, mixing the surfactant and the water to obtain a material B, and mixing the material A and the material B to obtain a material C.
According to a preferred embodiment of the present invention, the carrier precursor is mixed with the surfactant, followed by the extrusion molding, and the obtained molded article is subjected to the water vapor treatment in the water vapor-containing atmosphere without being dried. The inventor of the invention finds that when a surfactant is used in the preparation process of the carrier, preferably after extrusion molding, the obtained molded object is not dried but directly subjected to steam treatment, so that not only is energy consumption saved, but also in the steam treatment process, moisture carried by the molded object can be slowly evaporated and released, the pore expansion is facilitated, and the performance of the obtained carrier is more excellent.
According to a preferred embodiment of the present invention, the conditions of the extrusion molding include: the extrusion temperature is 40 to 90 ℃ and preferably 45 to 80 ℃. In the present invention, any method may be employed so that the temperature of extrusion is 40 to 90 ℃, preferably 45 to 80 ℃, for example, when the carrier precursor is mixed with water, extrusion aid and peptizing agent, and optionally a surfactant, the temperature of the extruded mixture is controlled by adjusting the temperature of water; or in the aforementioned mixture or C material, the weight ratio of water to the carrier precursor is 0.5-1.8:1, more preferably 0.55-1.5:1, the amount of the extrusion aid is 0.1-6 parts by weight, more preferably 2-4 parts by weight, and the amount of the peptizing agent is 0.1-6 parts by weight, more preferably 0.6-4 parts by weight, based on 100 parts by weight of the carrier precursor, the amount ratio of the components is adjusted so that the extrusion pressure of the mixture during extrusion is increased, usually the extrusion pressure is increased to 150-.
In the invention, the carrier precursor can be extruded into strips with various geometric shapes according to actual requirements. For example, the molded article obtained by extrusion molding may be a butterfly shape, a cylindrical shape, a clover shape, a honeycomb shape, a raschig ring shape, or the like, and preferably a butterfly shape and/or a clover shape. The catalyst support particle size is not particularly limited in the present invention on the premise that it is sufficient for the use in a reactor, and it is preferable that the shaped article has a length of 1 to 8mm, more preferably 2 to 6mm, and an aspect ratio of 1 to 8, preferably 2 to 6. The length-diameter ratio refers to the ratio of the length of the formed product to the diameter of the radial section of the strip formed product, and the diameter of the radial section is the diameter of a circumscribed circle of the section.
In the present invention, the steam treatment may be carried out by subjecting the molded article to a heat treatment in an atmosphere containing steam, and for example, the steam treatment may be carried out while continuously introducing an atmosphere containing steam into the container filled with the molded article.
In the present invention, the atmosphere containing water vapor may be entirely water vapor. The water vapor-containing atmosphere may also contain an oxygen-containing atmosphere, such as air.
According to a preferred embodiment of the invention, the water vapour content of the atmosphere containing water vapour is between 50 and 100% by volume.
According to a preferred embodiment of the invention, the water vapour-containing atmosphere contains water vapour and air, the water vapour content being between 50 and 90 vol.%, more preferably between 60 and 80 vol.%. In the research process, the invention discovers that the steam treatment of the formed product by the atmosphere containing steam and air with the preferred steam content is more beneficial to the increase of the average pore diameter of the carrier.
According to a preferred embodiment of the present invention, the conditions of the water vapor treatment include: the temperature is 400-700 ℃, the further optimization is 500-650 ℃, the time is 1-10h, the further optimization is 2-6h, the air volume space velocity is 200-3000h-1More preferably 200--1More preferably 300-800h-1. It is to be noted that the temperature, time and air volume space velocity of the water vapor treatment do not act independently, but affect the physicochemical properties of the carrier.
According to the method provided by the invention, the molded object can be subjected to roasting (the roasting condition can comprise that the temperature is 350-700 ℃, preferably 400-600 ℃ and the time is 1-10 hours, preferably 2-6 hours) and then subjected to water vapor treatment in the atmosphere containing water vapor, the molded object can also be directly subjected to water vapor treatment in the atmosphere containing water vapor without roasting, the invention is not particularly limited to this, and the molded object is preferably subjected to water vapor treatment without roasting (if drying is included, the molded object is dried and then subjected to the water vapor treatment).
The invention also provides a carrier prepared by the preparation method.
The carrier prepared by the preparation method is particularly suitable for a Fischer-Tropsch synthesis catalyst, and the Fischer-Tropsch synthesis catalyst prepared by the carrier provided by the invention is used in the Fischer-Tropsch synthesis process, and has high activity, selectivity and stability.
The invention also provides a Fischer-Tropsch synthesis catalyst, which comprises a carrier and an active metal component Co loaded on the carrier, wherein the carrier is provided by the invention.
This process can be carried out by any conventional method as long as the active metal component Co is supported on the carrier, and the present invention is not particularly limited thereto. For example, an impregnation method may be employed in which a cobalt-containing compound is prepared as an aqueous impregnation solution, and then the alumina support is impregnated with the aqueous impregnation solution, followed by drying and calcination. Wherein, the cobalt-containing compound is selected from water-soluble cobalt-containing compounds, and can be at least one of cobalt nitrate, cobalt acetate and cobalt formate.
The content of the active metal component Co in the catalyst is not particularly limited in the present invention, and for example, the content of the active metal component Co in terms of oxide is 2 to 20% by weight, preferably 3 to 15% by weight, and more preferably 4 to 12% by weight, based on the total weight of the catalyst.
According to the catalyst provided by the invention, an auxiliary agent can be introduced into the catalyst according to the needs, wherein the auxiliary agent is selected from one or more of Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Zr, Ti, Re, Hf, Ce, Mn, Fe, V and noble metals (such as Pt, Pd, Rh, Ir and Ru).
The method for introducing the assistant is not particularly limited in the present invention, and the assistant may be introduced before the active metal component Co is impregnated, may be introduced after the active metal component Co is impregnated, or may be introduced by Co-impregnation with the active metal component Co.
According to a preferred embodiment of the invention, the auxiliary agent is Zr.
The amount of the promoter used in the present invention is not particularly limited, and preferably the promoter is used in an amount such that the content of the promoter in terms of oxide is 0.01 to 30% by weight, preferably 0.05 to 15% by weight, based on the total weight of the catalyst.
The invention also provides a Fischer-Tropsch synthesis method, which comprises the step of contacting the synthesis gas with the catalyst under the Fischer-Tropsch synthesis reaction condition, wherein the catalyst is the Fischer-Tropsch synthesis catalyst provided by the invention.
According to the catalyst provided by the invention, before use, the active metal component in an oxidation state is subjected to reduction activation, preferably in the presence of hydrogen. The conditions for reductive activation may include: the reduction temperature may be 100 ℃ to 800 ℃, preferably 200 ℃ to 600 ℃, more preferably 300 ℃ to 450 ℃, the reduction time may be 0.5 to 72 hours, preferably 1 to 24 hours, more preferably 2 to 8 hours, the reduction activation may be performed in pure hydrogen, or may be performed in a mixed gas of hydrogen and an inert gas, such as a mixed gas of hydrogen and nitrogen and/or argon, and the hydrogen pressure may be 0.1 to 4MPa, preferably 0.1 to 2MPa, the inert gas refers to a gas that does not participate in the chemical reaction under the conditions of the present invention, such as nitrogen and a group zero element gas.
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
And respectively measuring the pore volume, the average pore diameter and the specific surface area of the carrier by adopting a BET low-temperature nitrogen adsorption method.
In the following examples and comparative examples, PEG400, PEG1000, PEG6000 were commercially available from beijing chemical plant; PVP is commercially available from Beijing chemical plant under the trademark PVP-K30.
Preparation example 1
(1) The preparation method comprises the steps of mixing 200 g of pseudo-boehmite powder with the particle diameter of 10-120 mu m and 6g of sesbania powder, taking nitric acid with the mass concentration of 68% as a peptizing agent, adding metered nitric acid into metered water, uniformly stirring, wherein the weight ratio of water to an alumina precursor is 0.5, uniformly mixing the mixture to obtain a material A, mixing PVP and metered water to obtain a material B, adding the material B into the material A to obtain a material C, wherein in the material C, the weight ratio of water to the alumina precursor is 0.7, the amount of the extrusion aid is 3 parts by weight, the amount of the peptizing agent (counted by nitric acid) is 1.33 parts by weight, and the amount of the PVP is 1 part by weight based on 100 parts by weight of the alumina precursor. And (3) kneading the material C on a kneading machine, and extruding a butterfly strip with the thickness of 1.4 mm on a screw rod type extruding machine, wherein the extrusion temperature is 65 ℃, and the extrusion pressure is 300 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise:when the volume ratio of the water vapor to the air is 75: under the atmosphere of 25, the volume space velocity of air is 700h-1And treating at 600 ℃ for 4h to obtain a carrier A1, wherein the pore volume, the average pore diameter and the specific surface area of the carrier are shown in Table 1.
Comparative preparation example 1
According to the method of preparation example 1, except that, in the step (2), the formed product is not subjected to steam treatment, but the formed product is directly put into an oven to be dried at 120 ℃ for 4 hours and then is directly roasted, the roasting temperature is 600 ℃ and the roasting time is 4 hours, the roasting is carried out under the circulation of air, and the volume space velocity of the air is 300 hours-1Thus, a carrier D1 was obtained, and the pore volume, average pore diameter and specific surface area of the carrier are shown in Table 1.
Preparation example 2
(1) Mixing 200 g of pseudo-boehmite powder with the particle diameter of 10-120 mu m and 6g of sesbania powder, adding 68% by mass of nitric acid serving as a peptizing agent into metered water, uniformly stirring, wherein the weight ratio of water to an alumina precursor is 0.5, uniformly mixing the mixture to obtain a material A, stirring and mixing PEG1000 and metered water to obtain a material B, and adding the material B into the material A to obtain a material C, wherein in the material C, the weight ratio of water to the alumina precursor is 0.74, the amount of the extrusion aid is 3 parts by weight, the amount of the peptizing agent (calculated by nitric acid) is 1.15 parts by weight, and the amount of the PEG1000 is 2 parts by weight based on 100 parts by weight of the alumina precursor. And (3) kneading the material C on a kneading machine, and extruding a butterfly strip with the thickness of 1.4 mm on a screw rod type extruding machine, wherein the extrusion temperature is 55 ℃, and the extrusion pressure is 280 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise: when the volume ratio of the water vapor to the air is 65: 35, the volume space velocity of air is 500h-1And the temperature is 590 ℃ for 4h, so that a carrier A2 is obtained, and the pore volume, the average pore diameter and the specific surface area of the carrier are shown in Table 1.
Preparation example 3
(1) 200 g of pseudo-boehmite powder with the particle diameter of 10-120 mu m and 6g of sesbania powder are mixed, then an aluminum nitrate aqueous solution (5.56 g of aluminum nitrate and 100 ml of water) is added to obtain a material A, PVP (polyvinyl pyrrolidone) and metered water are mixed to obtain a material B, and the material B is added to the material A to obtain a material C, wherein in the material C, the weight ratio of water to an alumina precursor is 0.68, the amount of the extrusion aid is 3 parts by weight based on 100 parts by weight of the alumina precursor, the amount of the peptizer (calculated by the aluminum nitrate) is 2.78 parts by weight, and the amount of the PVP is 1 part by weight. And (3) kneading the material C on a kneading machine, and extruding a butterfly strip with the thickness of 1.4 mm on a screw rod type extruding machine, wherein the extrusion temperature is 60 ℃, and the extrusion pressure is 290 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise: when the volume ratio of the water vapor to the air is 75: under the atmosphere of 25, the volume space velocity of air is 400h-1And treating at 620 ℃ for 4h to obtain a carrier A3, wherein the pore volume, the average pore diameter and the specific surface area of the carrier are shown in Table 1.
Comparative preparation example 2
The process of preparation example 3 was followed except that, in the step (2), the molded article was directly put into an oven to be dried at 120 ℃ for 4 hours, and then the dried product was directly calcined at 620 ℃ for 4 hours under the circulation of air at a volumetric space velocity of 400 hours without subjecting the dried product to steam treatment-1Thus, a carrier D2 was obtained, and the pore volume, average pore diameter and specific surface area of the carrier are shown in Table 1.
Preparation example 4
(1) Mixing 200 g of pseudo-boehmite powder (purchased from Sasol company, hereinafter referred to as Sasol powder) with the particle diameter of 10-120 mu m, wherein the amount of a sulfur-containing compound of the powder is less than 1000 mu g/g, the pore volume, the average pore diameter and the specific surface area are listed in Table 1, the same below) and 6g of sesbania powder (purchased from vegetable gum factory in Lanceo, Henan, the same below), taking nitric acid with the mass concentration of 68% as a peptizing agent, adding metered nitric acid into metered water, uniformly stirring, wherein the weight ratio of water to an alumina precursor is 0.5, uniformly mixing the mixture to obtain a material A, stirring and mixing 400 PEG and metered water to obtain a material B, adding the material B into the material A to obtain a material C, wherein the weight ratio of water to the alumina precursor in the material C is 0.7, and the extrusion assistant is used in 3 parts by weight per 100 parts by weight of the alumina precursor, the amount of peptizing agent (calculated by nitric acid) is 1.33 parts by weight, and the amount of PEG400 is 5 parts by weight. The material C was kneaded in a kneader and then extruded into 1.4 mm butterfly bars in a screw extruder (type F-26, available from general scientific and technical industries of southern university, hereinafter the same) at 65 ℃ and 300 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise: in the volume ratio of water vapor to air of 1: 1, the volume space velocity of air is 300h-1And treating at 550 ℃ for 4h to obtain a carrier A4, wherein the pore volume, the average pore diameter and the specific surface area of the carrier are shown in Table 1.
Preparation example 5
The process of preparation example 1 was followed except that, in step (2), the molded product was directly put into an oven to be dried at 120 ℃ for 4 hours, and then the dried product was subjected to the steam treatment to obtain support A5, the pore volume, average pore diameter and specific surface area of which are shown in Table 1.
Preparation example 6
(1) Mixing 200 g of pseudo-boehmite powder with the particle diameter of 10-120 mu m and 6g of sesbania powder, adding 68% by mass of nitric acid serving as a peptizing agent into metered water, uniformly stirring, wherein the weight ratio of water to an alumina precursor is 0.5, uniformly mixing the mixture to obtain a material A, mixing PEG6000 and metered water to obtain a material B, and adding the material B into the material A to obtain a material C, wherein in the material C, the weight ratio of water to the alumina precursor is 0.7, the amount of the extrusion aid is 3 parts by weight, the amount of the peptizing agent (calculated by nitric acid) is 1.33 parts by weight, and the amount of the PEG6000 is 1 part by weight based on 100 parts by weight of the alumina precursor. And (3) kneading the material C on a kneading machine, and extruding a butterfly strip with the thickness of 1.4 mm on a screw rod type extruding machine, wherein the extrusion temperature is 65 ℃, and the extrusion pressure is 300 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise: no air is introduced, only water vapor is introduced, and the volume space velocity of the water vapor is 300h-1At a temperature of 600 ℃ for 4 hours, support A6 was obtained, the pore volume, the average pore diameter and the specific surface area of which are shown in Table 1.
Preparation example 7
(1) Mixing 140 g of pseudo-boehmite powder with the particle diameter of 10-120 mu m, 60 g of Beta molecular sieve (purchased from catalyst Changling division company, the micropore volume of which is 0.052mL/g) and 6g of sesbania powder (purchased from vegetable gum factory in Lankano county, Henan, the same below), taking nitric acid with the mass concentration of 68% as a peptizing agent, adding metered nitric acid into metered water, stirring uniformly, wherein the weight ratio of water to an alumina precursor is 0.5, mixing the mixture uniformly to obtain a material A, mixing PVP with metered water to obtain a material B, adding the material B into the material A to obtain a material C, wherein, in the material C, the weight ratio of water to the carrier precursor is 0.74, and each 100 parts by weight of the carrier precursor is taken as a reference, the extrusion aid is 3 parts by weight, the peptizing agent (calculated by nitric acid) is 1.15 parts by weight, and the PVP is 2 parts by weight. And (3) kneading the material C on a kneading machine, and extruding a butterfly strip with the thickness of 1.4 mm on a screw rod type extruding machine, wherein the extrusion temperature is 65 ℃, and the extrusion pressure is 300 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise: when the volume ratio of the water vapor to the air is 70: under the atmosphere of 30, the volume space velocity of air is 500h-1And treating at 600 ℃ for 4h to obtain a carrier A7, wherein the pore volume, the average pore diameter and the specific surface area of the carrier are shown in Table 1.
Comparative preparation example 3
The process of preparation example 7 was followed except that, in step (2), the temperature of the steam treatment in the steam treatment was 800 ℃ to obtain a carrier D3.
Due to the fact that the water vapor treatment temperature is too high, the molecular sieve crystal lattice collapses, and the micropore volume of the molecular sieve is changed from 0.052mL/g to 0.011 mL/g.
Preparation example 8
According to the method of preparation 1, except that during the preparation of the support, no surfactant is used, specifically:
(1) 200 g of pseudo-boehmite powder with the particle diameter of 10-120 mu m and 6g of sesbania powder are mixed, nitric acid with the mass concentration of 68% is used as a peptizing agent, the metered nitric acid is added into metered water and stirred uniformly, the weight ratio of the water to an alumina precursor is 0.7, the amount of the extrusion aid is 3 parts by weight and the amount of the peptizing agent (counted by the nitric acid) is 1.33 parts by weight based on 100 parts by weight of the alumina precursor, and the mixture is mixed uniformly to obtain a mixed material. And (3) mixing and kneading the mixed material on a mixing and kneading machine, and extruding a 1.4 mm butterfly strip on a screw rod type extruding machine, wherein the extrusion temperature is 65 ℃, and the extrusion pressure is 300 Kgf.
(2) Introducing an atmosphere containing water vapor into the formed product to perform water vapor treatment, wherein the water vapor treatment conditions comprise: when the volume ratio of the water vapor to the air is 75: under the atmosphere of 25, the volume space velocity of air is 700h-1And treating at 600 ℃ for 4h to obtain a carrier A8, wherein the pore volume, the average pore diameter and the specific surface area of the carrier are shown in Table 1.
Comparative preparation example 4
The process of preparation example 8 was followed except that, in step (1), water was added to the mixture in such an amount that the weight ratio of water to the alumina precursor was 1.6, the extrusion temperature was 30 ℃ and the extrusion pressure was 80Kgf, to obtain a carrier D4, the pore volume, average pore diameter and specific surface area of which are shown in Table 1.
Comparative preparation example 5
According to the method of preparation example 8, except that, in the step (1), the peptizing agent (in terms of nitric acid) was used in an amount of 0.4 parts by weight, the extrusion temperature was 45 ℃ and the extrusion pressure was 200Kgf, with respect to 100 parts by weight of the alumina precursor, in the mixed materials, the support D5 was obtained, and the pore volume, the average pore diameter and the specific surface area of the support are shown in Table 1.
Comparative preparation example 6
According to the method of production example 8, except that the molded article of step (2) was not directly put into an oven, but was left at room temperature (25 ℃ C.) for 24 hours and then put into an oven, drying and steam treatment as described in production example 1 were carried out to obtain support D6, the pore volume, average pore diameter and specific surface area of which are shown in Table 1.
Preparation example 9
The process of preparation example 1 was followed except that, in step (2), the volume ratio of water vapor to air in the water vapor treatment process was 20: 80, support A9 was obtained, the pore volume, average pore diameter and specific surface area of which are shown in Table 1.
TABLE 1
Example 1
10g of the supports obtained in the above-mentioned preparation examples and comparative preparation examples were immersed in 7.5 ml of a 3.6 mol/l cobalt nitrate solution for 4 hours, and then the solid obtained by the immersion was dried at 120 ℃ for 2 hours and calcined at 400 ℃ for 4 hours to obtain a cobalt-based catalyst in which the content of Co, an active metal component, was 16.8% by weight in terms of oxide.
Test example 1
The catalysts obtained from the supports prepared in the above preparation examples and comparative preparation examples were tested for their performance by the following methods.
The test procedure was carried out in a fixed bed fischer-tropsch synthesis reactor with 5mL of catalyst.
The catalyst is reduced prior to use. The reduction is carried out at atmospheric pressure, with the other conditions being: the hydrogen flow was 1000NL/(g-cat h) (representing a flow of 1000 normal liters per hour per gram of catalyst), and the temperature was raised to 400 ℃ at a rate of 4 ℃/min and held for 5 h.
At 200 deg.C and 2.5MPa for 2000 hr-1Gas Hourly Space Velocity (GHSV) of H into the fixed bed reactor2Mixed gas (H) with CO2Mole ratio of 2/CO), conversion to CO (X) after 20h of reactionCO)、C5Above (containing C)5) Selectivity of hydrocarbonsCH4Selectivity of (2)And CO2Selectivity of (2)The tests were carried out and the results are given in Table 2. Wherein,
wherein, V1And V2Respectively representing the volume of feed gas entering the reaction system and the volume of tail gas flowing out of the reaction system in a certain time period under a standard condition; c. C1And c2Respectively representing the content of corresponding substances in the feed gas and the tail gas. n isconThe mole number of CO participating in the reaction through the reaction bed layer in a certain period of time,to convert into CO2The number of moles of CO of (a),to convert into CH4The number of moles of CO of (a),to convert into CH4、C2Hydrocarbons, C3Hydrocarbons, and C4Moles of CO of the hydrocarbon.
TABLE 2
Test example 2
This test example was conducted to test the stability of the catalysts obtained from the carriers obtained in the above preparation example 1 and comparative preparation example 1. The results are shown in Table 3.
The procedure of test example 1 was followed, except that the conversion of CO (X) was carried out after 200hCO)、C5Above (containing C)5) Selectivity of hydrocarbonsCH4Selectivity of (2)And CO2Selectivity of (2)And (6) carrying out testing.
TABLE 3
As can be seen from tables 2 and 3, the catalyst prepared by using the carrier provided by the invention has improved catalytic activity and C in Fischer-Tropsch synthesis reaction5+The selectivity and stability of the hydrocarbons are improved, and the selectivity of carbon dioxide and methane is obviously reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method of preparing a support, the method comprising:
extruding a carrier precursor to form strips, obtaining a formed object, carrying out steam treatment on the formed object in an atmosphere containing steam to obtain a carrier, wherein the average pore diameter of the prepared carrier is increased compared with that of the carrier precursor by the strip extrusion forming mode, the steam treatment condition and the type of the carrier precursor, and the increase △ n is at least represented by BET low-temperature nitrogen adsorption△ n is n2-n1, n1 is the average pore diameter of the carrier precursor, and n2 is the average pore diameter of the prepared carrier.
2. The method of claim 1, wherein the increase △ n isPreferably, it is
3. The production method according to claim 1, wherein the support precursor is pseudoboehmite;
preferably, the pseudoboehmite has an average pore diameter of
Further preferably, the pseudoboehmite does not contain a sulfur-containing compound.
4. The production method according to any one of claims 1 to 3, wherein the manner of extruding the carrier precursor includes: mixing a carrier precursor, water, an extrusion aid and a peptizing agent, and extruding the obtained mixed material into strips in a strip extruding machine for forming, wherein the weight ratio of the water to the carrier precursor in the mixed material is 0.5-1.8:1, preferably 0.55-1.5: 1; relative to 100 parts by weight of carrier precursor, the extrusion aid is 0.1-6 parts by weight, preferably 2-4 parts by weight, and the peptizing agent is 0.1-6 parts by weight, preferably 0.6-4 parts by weight;
preferably, the plodder is a screw-type plodder.
5. The method of claim 4, further comprising: drying the molded product, and then performing the water vapor treatment in an atmosphere containing water vapor;
preferably, the drying comprises drying the shape within 0 to 10 hours, preferably within 0 to 5 hours after extrusion;
preferably, the conditions of drying include: the temperature is 80-300 ℃, and the time is 0.5-12 hours; more preferably, the temperature is 120-; further preferably, the temperature is 140-.
6. The production method according to any one of claims 1 to 3, wherein the manner of extruding the carrier precursor includes: mixing a carrier precursor, a surfactant, water, an extrusion aid and a peptizing agent to obtain a material C, and extruding the material C into strips in a strip extruding machine for forming; in the material C, the weight ratio of water to the carrier precursor is 0.5-1.8:1, preferably 0.55-1.5: 1; relative to 100 parts by weight of carrier precursor, the extrusion aid is 0.1-6 parts by weight, preferably 2-4 parts by weight, the peptizing agent is 0.1-6 parts by weight, preferably 0.6-4 parts by weight, and the surfactant is 1-10 parts by weight, preferably 1-5 parts by weight;
preferably, the carrier precursor, the surfactant, the water, the extrusion aid and the peptizing agent are mixed in a manner comprising: mixing a carrier precursor, an extrusion aid, a peptizing agent and optional water to obtain a material A, mixing a surfactant with water and/or alcohol to obtain a material B, and mixing the material A and the material B to obtain a material C;
preferably, the surfactant is selected from at least one of a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a high molecular substance having surfactant characteristics.
7. The production method according to claim 6, wherein the carrier precursor is mixed with the surfactant and then subjected to the extrusion molding, and the obtained molded article is subjected to the water vapor treatment in the water vapor-containing atmosphere without being dried.
8. The production method according to any one of claims 4 to 7, wherein the conditions of the extrusion molding include: the extrusion temperature is 40 to 90 ℃ and preferably 45 to 80 ℃.
9. The production method according to any one of claims 1 to 6, wherein the water vapor content in the water vapor-containing atmosphere is 50 to 100% by volume;
preferably, the water vapour-containing atmosphere contains water vapour and air, the water vapour content being from 50 to 90% by volume, preferably from 60 to 80% by volume;
preferably, the conditions of the water vapor treatment include: the temperature is 400-700 ℃, preferably 500-650 ℃, the time is 1-10h, preferably 2-6h, and the air volume space velocity is 200-3000h-1Preferably 200--1More preferably 300--1。
10. A carrier produced by the production method according to any one of claims 1 to 9.
11. A fischer-tropsch synthesis catalyst comprising a support and an active metal component, Co, supported on the support, characterised in that the support is as claimed in claim 10.
12. The catalyst according to claim 11, wherein the active metal component Co is present in an amount of 2 to 20 wt.%, preferably 3 to 15 wt.%, more preferably 4 to 12 wt.%, calculated as oxide, based on the total weight of the catalyst.
13. A fischer-tropsch synthesis process comprising contacting synthesis gas with a catalyst under fischer-tropsch synthesis reaction conditions, wherein the catalyst is as claimed in claim 11 or claim 12.
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| CN112871155A (en) * | 2021-01-20 | 2021-06-01 | 陕西瑞科新材料股份有限公司 | Preparation method of zirconium dioxide based platinum oxide catalyst with shell-core structure |
| CN112871156A (en) * | 2021-01-20 | 2021-06-01 | 陕西瑞科新材料股份有限公司 | Preparation method of platinum oxide catalyst based on porous zirconia |
| CN112892512A (en) * | 2021-01-20 | 2021-06-04 | 陕西瑞科新材料股份有限公司 | Preparation method of porous zirconium dioxide carrier |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112871155A (en) * | 2021-01-20 | 2021-06-01 | 陕西瑞科新材料股份有限公司 | Preparation method of zirconium dioxide based platinum oxide catalyst with shell-core structure |
| CN112871156A (en) * | 2021-01-20 | 2021-06-01 | 陕西瑞科新材料股份有限公司 | Preparation method of platinum oxide catalyst based on porous zirconia |
| CN112892512A (en) * | 2021-01-20 | 2021-06-04 | 陕西瑞科新材料股份有限公司 | Preparation method of porous zirconium dioxide carrier |
| CN112871155B (en) * | 2021-01-20 | 2023-03-24 | 陕西瑞科新材料股份有限公司 | Preparation method of zirconium dioxide based platinum oxide catalyst with shell-core structure |
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