CN107570203B - Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof - Google Patents
Fischer-Tropsch synthesis naphtha conversion catalyst and preparation method thereof Download PDFInfo
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Abstract
A Fischer-Tropsch synthesis naphtha conversion catalyst comprises a carrier and active components with the following contents calculated by taking the carrier as a reference: 0.5-15.0 mass% of VA group element oxide and 0.1-2.0 mass% of rare earth element oxide, wherein the carrier comprises 40-75 mass% of ZSM-5 zeolite, 3-25 mass% of alumina and 8-35 mass% of amorphous aluminum silicate. The catalyst is used for aromatization reaction of Fischer-Tropsch synthesis naphtha, and has the advantages of high gasoline yield, good quality, long one-way service life and good regeneration performance.
Description
Technical Field
The invention relates to an aromatization catalyst and a preparation method thereof, in particular to a Fischer-Tropsch synthesis naphtha aromatization catalyst and a preparation method thereof.
Background
China is a country rich in coal, poor in oil and less in gas, and with the increasing shortage of petroleum resources in the world and the continuous improvement of the environmental protection requirements of people, the production of clean liquid fuel without sulfur, nitrogen and aromatic hydrocarbon from coal and natural gas by a Fischer-Tropsch (F-T) synthesis technology becomes the focus of wide attention in the industry. Although the F-T synthesis technology is industrialized, research reports on F-T synthesized crude oil processing catalysts and processing technology are few, and the F-T synthesized crude oil processing catalysts and processing technology have two main reasons: on the one hand, although crude fischer-tropsch synthesis differs greatly from crude oil, many of the existing mature petroleum processing technologies can be used for reference, such as: hydrogenation technology, cracking technology, reforming technology, separation technology and the like; on the other hand, many properties of crude products of F-T synthesis are still not recognized by many researchers.
Due to the different process routes of low-temperature F-T synthesis (LTFT) and high-temperature F-T synthesis (HTFT), the product distribution is greatly different. The operating temperature of the high-temperature process is about 350 ℃, a fluidized bed reactor is adopted, the synthesized main product is naphtha, and meanwhile, more low-carbon olefins are obtained and can be used as chemical raw materials. The operation temperature of the low-temperature process is about 250 ℃, a slurry bed and a fixed bed reactor are adopted, the main products are diesel oil and wax, and a small amount of low-carbon olefin and naphtha are simultaneously by-produced. With the increasing emphasis on environmental protection in various countries, not only the requirements on the contents of sulfur, nitrogen and aromatic hydrocarbons in the vehicle fuel are increased, but also the olefins in the oil products are drawing the attention of researchers. Because naphtha fractions obtained by high-temperature F-T synthesis and low-temperature F-T synthesis contain a large amount of olefins and oxygen-containing compounds, the naphtha fractions are not easy to be directly used as vehicle fuels, and high-added-value chemical products or high-quality gasoline components need to be obtained by further treatment.
At present, in the F-T synthesized naphtha fraction, except that 1-hexene and 1-octene can be separated to produce a high-value PAO product, other components can only enter a reforming device to produce gasoline after hydrofining treatment, the method has high hydrogen consumption and oxygen-containing compound loss, most of saturated olefins are straight-chain alkanes, the aromatic hydrocarbon potential is low, and the economic benefit is poor. The Fischer-Tropsch derived naphtha contains a large amount of olefin components and a small amount of oxygen-containing compounds, and can be used as a feedstock for the production of aromatic hydrocarbons or gasoline. Therefore, the method can be considered to produce gasoline fraction from the F-T synthesized naphtha through aromatization reaction under the condition of less liquid phase loss, properly reduce the olefin content of the gasoline, improve the content of isoparaffin and aromatic hydrocarbon, and simultaneously react the oxygen-containing compounds to generate gasoline and water, thereby improving the quality of the gasoline, and the gasoline can be used as a high-octane blending component or a gasoline product to be directly delivered from a factory. However, because the amount of carbon deposition in the conversion of gasoline with high olefin content is extremely high, the catalyst is required to have good carbon deposition resistance, and the catalyst is required to have excellent hydrothermal stability in the reaction of oxygen-containing compounds, the catalyst for the aromatization reaction of the raw material has corresponding characteristics and properties.
The research paper of "processing and utilization of Fischer-Tropsch synthetic oil" is reported in volume 36, No. 1 of 2006, refining technology and engineering, and the properties of Fischer-Tropsch synthetic oil and the processing and utilization ways of each fraction thereof are introduced. The main product synthesized by the high-temperature method F-T is gasoline and simultaneously has more low-carbon olefins; the main products of F-T synthesis by low temperature method are diesel oil and wax, and a small amount of olefin and chemicals are produced as by-products. Naphtha fraction of F-T synthetic oil has high alkane content and low impurity content, and is not suitable for gasoline fraction but can be used as high-quality ethylene plant raw material.
The research article of "research progress of F-T synthetic oil processing technology" was reported in the journal of fuel chemistry 2009, volume 37, phase 6, and a review is made on the research of F-T synthetic crude oil processing technology in recent years. According to the characteristics of the F-T synthetic product, the F-T synthetic product can be used for producing a plurality of high-quality solvent oils, lubricating oil, fuel oil and chemicals through the processes of superposition, hydrogenation, hydrocracking, oxidation, carbonylation and the like, and the existing petroleum processing technology and catalyst still need to be improved and optimized aiming at the characteristics of the F-T synthetic oil product.
the olefin is a first-grade product with remarkable value-increasing potential in high and low temperature F-T synthesized co-production products, including ethylene, propylene, butylene and linear α -olefin, and the olefin is taken as a raw material, preferably high-quality lubricating oil, C and linear α -olefin are taken as raw materials4～C10PAO and polypropylene are produced by the linear α -olefin as final target products.
The issued or published patents for F-T synthetic produced oil mainly surround the technology of hydrogenation treatment of Fischer-Tropsch synthetic produced oil, and comprise processes or catalysts for hydrogenation saturation and impurity removal of fractions such as Fischer-Tropsch synthetic naphtha, diesel oil and wax. At present, a technical process and related catalyst for directly converting and generating gasoline or diesel oil fractions by taking Fischer-Tropsch synthetic naphtha or part of diesel oil as a raw material without hydrotreating are not provided.
The patent of producing gasoline or aromatic hydrocarbon by taking light hydrocarbon or conventional naphtha as raw materials is more, and CN98101358.9 discloses a light hydrocarbon aromatization catalyst and a preparation method thereof, wherein the catalyst contains Zn, mixed rare earth and HZSM-5 components, the catalyst comprises 0.8-3.5 wt% of Zn, 0.2-1.5 wt% of mixed rare earth oxide and 95.0-99.0 wt% of carrier, the carrier comprises 50-80 wt% of HZSM-5 zeolite and 20-50 wt% of gamma-alumina, and the mixed rare earth contains elements such as lanthanum, cerium, praseodymium, neodymium and the like.
CN00122835.8 discloses a light hydrocarbon aromatization catalyst and a preparation method thereof, the catalyst comprises HZSM-5 zeolite, ZnO, a binder and a VA or VIB group metal oxide, the metal oxide is an oxide of bismuth, antimony or tungsten, and the binder is alumina or silica.
CN02143362.3 discloses a method for non-hydroaromatization and desulfurization of catalytically cracked gasoline, wherein the adopted molecular sieve in the catalyst can be one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y and Beta types, and contains one or more of rare earth elements, VIB and VIII group elements, halogen group elements, Mg, Zn, P and Na, and the content is 0.01-20%.
Disclosure of Invention
The invention aims to provide a Fischer-Tropsch synthesis naphtha conversion catalyst and a preparation method thereof.
The Fischer-Tropsch synthesis naphtha conversion catalyst provided by the invention comprises a carrier and active components with the following contents calculated by taking the carrier as a reference:
0.5 to 15.0 mass% of a VA group element oxide,
0.1 to 2.0 mass% of rare earth element oxide,
the carrier comprises 40-75 mass% of ZSM-5 zeolite, 3-25 mass% of alumina and 8-35 mass% of amorphous aluminum silicate.
The catalyst is prepared by loading a proper amount of VA group elements and rare earth elements on a carrier prepared from ZSM-5 zeolite, alumina and amorphous silica-alumina, can adapt to a high-temperature hydrothermal environment when used for converting Fischer-Tropsch synthesis naphtha, and has high reaction activity and long service life.
Drawings
Figure 1 is an XRD pattern of the catalyst prepared by the present invention.
Detailed Description
According to the invention, ZSM-5 zeolite is used as a main active component of the catalyst, alumina and silica sol are used as binders for molding and then are roasted to form a carrier containing alumina and amorphous alumina, so that the carrier strength is increased, the distribution of B acid and L acid is modulated, and the excessive aromatization reaction of olefin in the Fischer-Tropsch synthesis naphtha raw material can be inhibited. In addition, after VA group elements and rare earth elements are added into the catalyst for modification, the stability and the anti-carbon deposition capability of the catalyst are obviously improved, and the catalyst can adapt to high-temperature hydrothermal atmosphere caused by a large amount of water generated by oxygen-containing compounds contained in Fischer-Tropsch synthesis naphtha in the aromatization process, so that the catalyst keeps high activity in the environment and prolongs the one-way reaction life, and has good regeneration performance.
The catalyst provided by the invention solves the problem that the Fischer-Tropsch synthesis naphtha has no reasonable utilization means, and can produce more high-value products such as gasoline, liquefied gas and the like. By adopting the catalyst prepared by the invention, Fischer-Tropsch synthesis naphtha is used as a raw material, and under a certain reaction condition, a high-octane gasoline blending component (RON is more than or equal to 90) with the olefin content of not more than 5 mass%, the aromatic hydrocarbon content of not more than 50 mass% and the benzene content of less than 2 mass% can be obtained, and a small amount of high-quality liquefied gas component can be generated. The high-octane gasoline blending component produced by Fischer-Tropsch synthesis naphtha is blended with catalytic cracking gasoline with higher olefin content according to a certain proportion, and the olefin content of the catalytic cracking gasoline can be greatly reduced under the condition that the octane value RON of the finished gasoline is not less than 93, so that the gasoline meets the clean motor gasoline standard specified by national environmental protection.
The preferred active component contents of the catalyst of the invention are as follows:
1.5 to 7.0 mass% of a VA group element oxide,
0.2 to 1.5 mass% of a rare earth element oxide.
The carrier preferably comprises 45-75 mass% of ZSM-5 zeolite, 3-25 mass% of alumina and 10-30 mass% of amorphous aluminum silicate. Al in the amorphous aluminum silicate2O3The content of (B) is 35 to 37 mass%.
In the catalyst, the VA group element is phosphorus, antimony or bismuth. The rare earth element oxide can be one or more of lanthanum, cerium, praseodymium and neodymium, and is preferably a mixed rare earth oxide. The content of each metal in the mixed rare earth oxide is calculated by the oxide: 20-60% by mass of lanthanum oxide, 40-80% by mass of cerium oxide, 0-10% by mass of praseodymium oxide and 0-10% by mass of neodymium oxide, wherein the mixed rare earth oxide may contain no praseodymium oxide and no neodymium oxide, and if all four elements are contained, the contents thereof may be 20-40% by mass of lanthanum oxide, 40-60% by mass of cerium oxide, 10-18% by mass of praseodymium oxide and 2-10% by mass of neodymium oxide.
SiO of the ZSM-5 zeolite2/Al2O3The molar ratio of (b) is preferably 20 to 150, more preferably 30 to 100.
The alumina in the carrier is preferably gamma-Al2O3. The carrier can be in the shape of a strip, a pellet, a sheet, a particle or a microsphere, so as to be suitable for fixed bed, moving bed or fluidized bed reaction.
The preparation method of the catalyst provided by the invention comprises the following steps:
(1) mixing hydrogen type ZSM-5 zeolite, alumina and silica sol, forming, drying and roasting to obtain a carrier,
(2) carrying out water vapor treatment on the carrier at 450-700 ℃,
(3) and (3) impregnating the carrier treated by the water vapor with a compound containing VA group elements and a compound solution containing rare earth elements, and then drying and roasting.
In the method, the step (1) is carrier forming, and the hydrogen type ZSM-5 zeolite is mixed with alumina and silica sol and then formed. The molding can be extrusion molding, and can also be drop ball, rolling ball or tabletting molding. Preferably, the extrusion molding is carried out, and when the extrusion molding is carried out, a proper amount of peptizing agent is preferably added into the mixture for kneading and extrusion molding, wherein the peptizing agent is preferably dilute nitric acid solution. And drying and roasting the formed solid to obtain the carrier. The roasting temperature is 500-650 ℃, preferably 530-600 ℃, and the roasting time is preferably 1-10 hours, and more preferably 3-5 hours.
(2) the carrier prepared in the step (1) is subjected to steam treatment, wherein the steam treatment is to perform aging treatment on the catalyst by using 100% of steam so as to improve the stability and the regeneration performance of the catalyst, the steam treatment temperature is preferably 500-600 ℃, the steam treatment time is 0.5-8 hours, preferably 2-6 hours, and the α value of the carrier after the steam treatment is 10-100, preferably 20-60 (the α value is determined by referring to a petrochemical engineering analysis method (RIPP experimental method) published by Yangshui and the like, and the α value is determined by a P255 constant temperature method).
The steam treatment may also be carried out on the hydrogen form of the ZSM-5 zeolite prior to catalyst formation.
In the method of the invention, the VA element and the rare earth element are introduced into the carrier in the step (3), the compound containing the VA element is preferably phosphoric acid, antimony nitrate or bismuth acetate, and the compound containing the mixed rare earth element is preferably chloride or nitrate of mixed rare earth. The impregnation can be co-impregnation, namely mixing a compound solution containing the VA group element and a compound solution of mixed rare earth elements and then impregnating the carrier, or firstly impregnating the carrier with the VA group element compound solution, drying the impregnated solid, then impregnating the impregnated solid with the compound solution containing the rare earth elements, and then drying and roasting the impregnated solid. The drying temperature is preferably 80-140 ℃, more preferably 90-120 ℃, the drying time is preferably 5-30 hours, more preferably 8-24 hours, the roasting temperature is preferably 500-650 ℃, more preferably 530-600 ℃, the roasting time is preferably 1-10 hours, more preferably 3-5 hours,
the Fischer-Tropsch synthesis naphtha comprises 15-90% by mass of olefin, preferably 45-90% by mass, 1-20% by mass of oxygen-containing compound, preferably 5-30% by mass, and the oxygen-containing compound is mainly alcohol or ketone.
The catalyst is suitable for conversion reaction of Fischer-Tropsch synthetic naphtha under non-hydrogenation condition, and Fischer-Tropsch synthetic naphtha is subjected to a series of complex reactions such as superposition, hydrogen transfer, aromatization, alkylation and isomerization under the action of the catalyst to generate high-octane gasoline components and high-quality liquefied gas.
The method for carrying out Fischer-Tropsch synthesis naphtha aromatization by using the catalyst comprises the following steps: Fischer-Tropsch synthetic naphtha is added at 200-500 ℃, 0.1-2.0 MPa and feeding mass airspeed of 0.1-20.0 h-1Under the conditions of (1) and the present inventionThe catalyst is provided for contact reaction. The reaction temperature is preferably 300-380 ℃, the pressure is preferably 0.2-1.0 MPa, and the feeding mass space velocity is preferably 0.1-2.0 h-1。
The Fischer-Tropsch synthesis naphtha conversion reaction can adopt reactor types such as a fixed bed, a moving bed, a lifting pipe and the like. The raw materials do not need to be pre-refined, and a single fixed bed reactor is preferably adopted for reaction.
The catalyst of the invention can be repeatedly used by regeneration after being deactivated. The catalyst regeneration is carried out by using oxygen-containing inert gas, wherein the oxygen content is preferably 0.5-5.0 vol%, more preferably 0.5-2.5 vol%, and the inert gas is preferably nitrogen. The regeneration temperature is 400-500 ℃, the pressure is 0.1-3.0 MPa, and the gas/agent volume ratio is 250-1000.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
Comparative example 1
The catalyst was prepared according to the prior art.
(1) Preparing a carrier: taking SiO2/Al2O3130 g of HZSM-5 zeolite powder with the molar ratio of 56 and 70 g of pseudo-boehmite powder (produced by Sasol company of Germany and the content of alumina is 75 mass percent), 100g of nitric acid aqueous solution with the concentration of 1.0m percent is added for peptization, kneaded and extruded into strips with the diameter of 2 mm, the strips are cut into particles with the length of 2-3 mm when being dried for 4 hours at the temperature of 110 ℃, and the particles are roasted for 4 hours at the temperature of 550 ℃ to prepare the carrier.
(2) and (2) water vapor treatment, namely filling the carrier prepared in the step (1) into a tubular reactor, heating the carrier to 550 ℃ in air flow under the pressure of 0.1MPa, introducing water vapor for treatment for 4 hours to obtain the catalyst A, wherein the α value is 31, the composition of the catalyst A is shown in table 1, an XRD diffraction diagram is shown in table 1, and it can be seen that characteristic diffraction peaks of a ZSM-5 molecular sieve appear near 2 theta of 8 degrees, 9 degrees, 23 degrees, 24 degrees and 25 degrees respectively, and the acid amounts of B (Bronsted) acid and L (Lewis) acid are shown in table 2 under different temperatures by pyridine adsorption.
Comparative example 2
100g of the carrier treated with steam in the step (2) in the comparative example 1 was immersed in 50ml of a 100mg/ml phosphoric acid solution for 1 hour, the immersed solid was taken out and dried at 120 ℃ for 2 hours, and then 100ml of a 10mg/ml aqueous solution of a mixed rare earth chloride (containing 40 mass% of lanthanum oxide and 60 mass% of cerium oxide) was added and immersed at 80 ℃ for 2 hours, the immersed solid was taken out and dried at 120 ℃ for 8 hours, and calcined at 550 ℃ for 4 hours, whereby a catalyst K was obtained.
Example 1
The catalyst was prepared according to the process of the invention.
(1) Preparation of the support
Taking SiO2/Al2O3130 g of HZSM-5 zeolite powder with the molar ratio of 56, 35 g of pseudo-boehmite powder and 35 g of silica Sol (SiO)230 mass%), adding 100g of 1.0 m% nitric acid aqueous solution, stirring, standing to peptize, kneading, extruding into strips with diameter of 2 mm, drying at 110 deg.C for 4 hr, cutting into particles with length of 2-3 mm, and calcining at 550 deg.C for 4 hr to obtain carrier, wherein the alumina is gamma-Al2O3。
(2) Steam treatment
and (2) loading the carrier prepared in the step (1) into a tubular reactor, heating to 550 ℃ in air flow under 0.1MPa, and introducing water vapor for treatment for 4 hours, wherein the α value is 33.
(3) Preparation of the catalyst
Soaking 100g of the carrier treated by the water vapor in the step (2) in 50ml of 100mg/ml phosphoric acid solution for 1 hour, taking the soaked solid, drying the solid at 120 ℃ for 2 hours, then adding 100ml of mixed rare earth chloride (containing 40 mass percent of lanthanum oxide and 60 mass percent of cerium oxide) aqueous solution with the concentration of 10mg/ml, soaking the solid at 80 ℃ for 2 hours, taking the soaked solid, drying the solid at 120 ℃ for 8 hours, and roasting the solid at 550 ℃ for 4 hours to obtain a catalyst B, wherein the composition of the catalyst B is shown in Table 1, and the phosphorus content is P2O5And calculating the content of the mixed rare earth by the oxide of the mixed rare earth. The XRD diffractogram of catalyst B is shown in FIG. 1, and it can be seen that a new diffraction peak appears at around 20 ℃ 2. theta. which is a diffraction peak of amorphous alumino-silicate having an alumina content of 36.2 mass% (hereinafter the same), and the amounts of B (Bronsted) acid and L (Lewis) acid measured by pyridine adsorption at different temperatures are shown in Table 2.
Example 2
Preparation of the catalyst by the method of example 1Simultaneously (1) step of taking SiO2/Al2O3130 g of HZSM-5 zeolite powder with a molar ratio of 56, 50 g of pseudo-boehmite powder and 20 g of silica sol, 100g of nitric acid aqueous solution with the concentration of 1.0m percent is added for stirring, mixing, extruding, drying and roasting to prepare a carrier, the α value of the carrier is 35 after water vapor treatment, and the composition of the prepared catalyst C is shown in a table 1 after phosphorus and mixed rare earth are introduced by impregnation, an XRD diffraction pattern of the catalyst C is shown in a table 1, and it can be seen that a new diffraction peak appears near 20 degrees of 2 theta, the new diffraction peak is a diffraction peak of amorphous aluminosilicate, and the amounts of B (Bronsted) acid and L acid (Lewis) acid are shown in a table 2 when the B (Bronsted) acid and the L acid (Lewis) are detected by pyridine adsorption at different temperatures.
Example 3
The catalyst was prepared as in example 1, except that (1) SiO was taken2/Al2O3130 g of HZSM-5 zeolite powder with a molar ratio of 56, 20 g of pseudo-boehmite powder and 50 g of silica sol are added, 100g of nitric acid aqueous solution with the concentration of 1.0 m% is added, stirred, mixed, extruded, dried and roasted to prepare a carrier, the α value of the carrier is 34 after water vapor treatment, and then phosphorus and mixed rare earth are introduced through impregnation to prepare a catalyst D, the composition of which is shown in a table 1, an XRD diffraction diagram of the catalyst D is shown in a table 1, and it can be seen that a new diffraction peak appears near 20 degrees of 2 theta, the new diffraction peak is a diffraction peak of amorphous aluminosilicate, and the amounts of B (Bronsted) acid and L (Lewis) acid which are measured by pyridine adsorption at different temperatures are shown in a table 2.
Example 4
The catalyst was prepared as in example 1, except that (1) SiO was taken2/Al2O3the composition of a catalyst E prepared by adding 90 g of HZSM-5 zeolite powder with a molar ratio of 56, 55 g of pseudo-boehmite powder and 55 g of silica sol into 100g of nitric acid aqueous solution with a concentration of 1.0 m%, stirring, mixing, extruding, drying and roasting, wherein the α value of the carrier is 33 after being treated by water vapor, and then phosphorus and mixed rare earth are introduced by impregnation is shown in Table 1. the XRD diffraction pattern of the catalyst E is shown in FIG. 1. As can be seen, a new diffraction peak appears near 20 degrees of 2 theta, the new diffraction peak is the diffraction peak of amorphous aluminosilicate, and the amounts of B (Bronsted) acid and L acid (Lewis) acid measured by pyridine adsorption at different temperatures are shown in Table 2.
As can be seen from FIG. 1, in the present invention, a silica sol is introduced into alumina during the preparation of a carrier, amorphous aluminum silicate is generated in the carrier obtained after calcination, and the peak area of the amorphous aluminum silicate increases with the increase of the amount of the silica sol introduced, indicating that the amount of the formed amorphous aluminum silicate increases with the increase of the amount of the silica sol introduced.
As can be seen from Table 2, after amorphous aluminum silicate is formed in the carrier, the amount of acid on the catalyst changes with the increase of the content thereof, the ratio of the amount of L/B acid measured by pyridine adsorption at 200 ℃ decreases, indicating that the ratio of the amount of B acid increases, and the ratio of the amount of L/B acid measured by pyridine adsorption at 350 ℃ increases, indicating that the ratio of the amount of L acid increases.
Example 5
A catalyst was prepared as in example 1 except that (3) the carrier was impregnated with 50ml of a 100mg/ml phosphoric acid solution for 1 hour, the impregnated solid was dried at 120 ℃ for 2 hours, then impregnated with 100ml of a 20mg/ml mixed rare earth chloride aqueous solution at 80 ℃ for 2 hours, and the impregnated solid was dried and calcined to give catalyst F having the composition shown in Table 1.
Example 6
A catalyst was prepared as in example 1 except that (3) the carrier was impregnated with 50ml of a 40mg/ml phosphoric acid solution for 1 hour, the impregnated solid was dried at 120 ℃ for 2 hours, then impregnated with 100ml of a 10mg/ml mixed rare earth chloride aqueous solution at 80 ℃ for 2 hours, and the impregnated solid was dried and calcined to give catalyst G having the composition shown in Table 1.
Example 7
A catalyst was prepared as in example 1 except that (3) the carrier was impregnated with 50ml of a 200mg/ml phosphoric acid solution for 1 hour, the impregnated solid was dried at 120 ℃ for 2 hours, then impregnated with 100ml of a 10mg/ml mixed rare earth chloride aqueous solution at 80 ℃ for 2 hours, and the impregnated solid was dried and calcined to give catalyst H having the composition shown in Table 1.
Example 8
A catalyst was prepared as in example 1 except that (3) the carrier was impregnated with 50ml of a 40mg/ml antimony nitrate solution for 1 hour, the impregnated solid was dried at 120 ℃ for 2 hours, then impregnated with 100ml of a 10mg/ml mixed rare earth chloride aqueous solution at 80 ℃ for 2 hours, and the impregnated solid was dried and calcined to give catalyst I having the composition shown in Table 1.
Example 9
A catalyst was prepared as in example 1 except that (3) the carrier was impregnated with 50ml of a 40mg/ml bismuth acetate solution for 1 hour, the impregnated solid was dried at 120 ℃ for 2 hours, then impregnated with 100ml of a 10mg/ml mixed rare earth chloride aqueous solution at 80 ℃ for 2 hours, and the impregnated solid was dried and calcined to give catalyst J, the composition of which is shown in Table 1.
Examples 10 to 20
The following examples evaluate the reactivity of the catalysts.
The performances of the catalysts of the invention and the comparative catalysts were evaluated on a small fixed bed reactor using the Fischer-Tropsch synthesis naphtha shown in Table 3 as a raw material. The evaluation reaction conditions were: 340 ℃, 0.3MPa and the mass space velocity of the raw material is 0.5 hour-1The reaction time was 48 hours. The catalysts used and the reaction results for each example are shown in Table 4.
As can be seen from Table 4, the catalyst of the present invention has a significantly reduced amount of carbon deposition as compared with the comparative catalyst A, K, and the dry gas and C in the reaction product3+C4The yield is reduced, amorphous aluminum silicate contained in the carrier is more beneficial to the generation of aromatic hydrocarbon and isomeric hydrocarbon, C5The liquid yield is improved, which shows that the gasoline yield is improved, the aromatic hydrocarbon content in the liquid product is increased, and the octane number of the gasoline is improved accordingly.
Example 21
This example demonstrates the good stability of the catalyst of the invention.
A reactor of a small fixed bed reactor was charged with a catalyst F using Fischer-Tropsch naphtha shown in Table 2 as a raw material at a reaction pressure of 0.3MPa and a raw material mass space velocity of 1hr-1The reaction was continued for 800 hours, and the reaction results are shown in Table 5.
As can be seen from Table 5, the liquid-phase product yield was maintained at a high level over 800 hours, C5 +(i.e. gasoline) RONThe octane number is reduced from 93.2 at the beginning to 91.0 at the end of the reaction, and the average RON is more than 92.0, which shows that the catalyst of the invention has good aromatization activity and stability.
Example 22
This example examines the regeneration performance of the catalyst of the invention.
A reactor of a small fixed bed reactor was packed with a catalyst F, and a Fischer-Tropsch naphtha shown in Table 2 was used as a raw material to conduct a reaction under the following conditions: 340 deg.C, 0.3MPa, and material mass space velocity of 1.0hr-1And regenerating the catalyst after the continuous reaction for 100 hours.
The regeneration method comprises the following steps: introducing nitrogen with the oxygen content of 0.5-2.0 vol% into a catalyst bed layer, and regenerating the catalyst at the conditions of 400 ℃, 0.8MPa and the gas/agent volume ratio of 500. After regeneration, the catalyst is reacted again according to the above conditions for 100 hours. The catalyst was regenerated several times, each time for 100 hours, and the results are shown in Table 6.
As can be seen from Table 6, catalyst F of the present invention was regenerated 20 times and then treated with C5 +The yield of the liquid product is still very close to that before regeneration, which shows that the catalyst of the invention has good regeneration performance.
TABLE 1
TABLE 2
TABLE 3
Note: the other 9.05 mass% is an oxygen-containing compound, and mainly alcohols.
TABLE 4
TABLE 5
TABLE 6
| Number of times of catalyst regeneration | 0 | 10 | 20 |
| (H2+C1+C2) Yield, mass% | 0.48 | 0.46 | 0.39 |
| (C3+C4) Yield, mass% | 23.51 | 23.22 | 21.96 |
| C5 +Yield, mass% | 76.01 | 76.32 | 77.65 |
| C5 +Content of aromatic hydrocarbons in the oil | 35.65 | 34.80 | 33.96 |
| C5 +The content of the benzene in the total mass percent | 0.98 | 0.96 | 0.95 |
| C5 +Content of medium olefin, mass% | 5.25 | 5.76 | 6.01 |
| C5 +RON | 93.2 | 92.8 | 92.4 |
Claims (11)
1. A Fischer-Tropsch synthesis naphtha conversion catalyst comprises a carrier and active components with the following contents calculated by taking the carrier as a reference:
0.5 to 15.0 mass% of a VA group element oxide,
0.1 to 2.0 mass% of rare earth element oxide,
the carrier comprises 40-75 mass% of ZSM-5 zeolite, 3-25 mass% of alumina and 8-35 mass% of amorphous aluminum silicate.
2. The catalyst according to claim 1, characterized in that the active component content of the catalyst is as follows:
1.5 to 12.0 mass% of a VA group element oxide,
0.2 to 1.5 mass% of a rare earth element oxide.
3. The catalyst according to claim 1 or 2, wherein the carrier comprises 45 to 75 mass% of ZSM-5 zeolite, 3 to 25 mass% of alumina, and 10 to 30 mass% of amorphous aluminum silicate.
4. The catalyst of claim 1 or 2 wherein the group VA element is phosphorus, antimony or bismuth.
5. The catalyst according to claim 1 or 2, wherein the rare earth element oxide is a mixed rare earth oxide.
6. The catalyst according to claim 1 or 2, characterized in that the SiO of the ZSM-5 zeolite2/Al2O3The molar ratio is 20-150.
7. A catalyst according to claim 1 or 2, characterised in that the alumina is γ -Al2O3。
8. A method of preparing the catalyst of claim 1, comprising the steps of:
(1) mixing hydrogen type ZSM-5 zeolite, alumina and silica sol, forming, drying and roasting to obtain a carrier,
(2) carrying out water vapor treatment on the carrier at 450-700 ℃,
(3) and (3) impregnating the carrier treated by the water vapor with a compound containing VA group elements and a compound solution containing rare earth elements, and then drying and roasting.
9. The method according to claim 8, wherein the calcination temperature in step (1) is 500 to 650 ℃.
10. the method according to claim 8, wherein the carrier after the steam treatment in the step (2) has an α value of 10 to 100.
11. The method according to claim 8, wherein the compound containing a group VA element used in step (3) is phosphoric acid, antimony nitrate or bismuth acetate, and the compound containing a rare earth element is a chloride or nitrate of a misch metal.
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| EP0909582A1 (en) * | 1997-10-15 | 1999-04-21 | China Petro-Chemical Corporation | Cracking catalytic for the production of light olefins and its preparation |
| CN101590421A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | The catalyst of a kind of olefin catalytic cracking to produce propylene and ethene and application thereof |
| CN102500409A (en) * | 2011-09-28 | 2012-06-20 | 大连理工大学 | Gasoline aromatization and isomerization reforming catalyst and preparation method and applications thereof |
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| EP0909582A1 (en) * | 1997-10-15 | 1999-04-21 | China Petro-Chemical Corporation | Cracking catalytic for the production of light olefins and its preparation |
| CN101590421A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | The catalyst of a kind of olefin catalytic cracking to produce propylene and ethene and application thereof |
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