CN115957800A

CN115957800A - Catalyst for processing light hydrocarbon, preparation method and regeneration method thereof, and method for processing light hydrocarbon

Info

Publication number: CN115957800A
Application number: CN202111172214.3A
Authority: CN
Inventors: 王子健; 于中伟; 马爱增; 王杰广; 刘洪全; 孔令江
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2021-10-08
Filing date: 2021-10-08
Publication date: 2023-04-14

Abstract

The invention relates to the technical field of catalysts, in particular to a catalyst for processing light hydrocarbon, a preparation method and a regeneration method thereof, and a method for processing light hydrocarbon. The catalyst comprises a composite carrier, sulfate and an active component, wherein the sulfate and the active component are loaded on the composite carrier, and the active component comprises rare earth elements and/or VA group elements; the composite support contains 10-50wt% of a hydrogen-type ZSM-5 zeolite, 5-40wt% of zirconia, and 10-85wt% of alumina, based on the total weight of the composite support. The catalyst has high catalytic stability and regeneration performance, can be used for processing light hydrocarbon, particularly light naphtha, can produce aromatic hydrocarbon and by-product low-carbon olefin, and obtains high aromatic hydrocarbon yield and low-carbon olefin yield, and meanwhile, has strong carbon deposition resistance and long one-way reaction period.

Description

Catalyst for processing light hydrocarbon, preparation method and regeneration method thereof, and method for processing light hydrocarbon

Technical Field

The invention relates to the technical field of catalysts, and particularly relates to a catalyst for processing light hydrocarbon, a preparation method and a regeneration method thereof, and a method for processing light hydrocarbon.

Background

Light naphtha is typically C byproduct from petroleum and coal processing ₄ ～C ₇ The main sources of the low-carbon hydrocarbon mixture are the following: c of catalytic cracking, hydrocracking and coking unit ₄₊ Component, cracking C of an ethylene cracking plant ₅₊ The components, such as the topping oil, raffinate oil and other fractions of the catalytic reforming and aromatic hydrocarbon extraction combined device are limited gradually along with the further limitation of the steam pressure of the new gasoline standard due to the very high steam pressure of the light hydrocarbon components, and a new utilization way is urgently needed to be found. Meanwhile, with the development of the oil refining industry technology in China and the continuous expansion of the processing scale of crude oil, the processing depth of the crude oil is increasingly improved, and the crude oil is produced from refinery C ₄ ～C ₇ Is mainly composed ofThe light hydrocarbon resources are more and more, the light hydrocarbon resources are converted into high-value chemical products such as aromatic hydrocarbon, low-carbon olefin and the like, the utilization benefit of the light hydrocarbon is greatly improved, and the method has important significance for conversion of refining enterprises to chemical industry.

In recent years, various researches are carried out around the utilization of light hydrocarbons at home and abroad, wherein the light hydrocarbon aromatization technology is developed rapidly, the light hydrocarbon aromatization technology developed at present comprises the processes of Alpha Process in Japan, cyclic Process developed by UOP/BP combination, Z-forming in Japan and the like, and the light hydrocarbon aromatization developed at home also realizes wide industrial application. On the background, there are also related research reports on the simultaneous production of aromatic hydrocarbons and light olefins from light hydrocarbons.

CN1065901C firstly provides a method for simultaneously converting non-aromatic hydrocarbon into aromatic hydrocarbon and olefin, and adopts a zeolite catalyst modified by silicon, boron, phosphorus and alkaline earth metal and subjected to special post-treatment, so that the yield of aromatic hydrocarbon and light olefin in the aromatization process is improved while the coke formation rate is reduced; meanwhile, in the aspect of process research, the partial pressure of reactants is reduced by adding an inert medium, and the yield of light olefins is further improved.

CN1504541A discloses a catalyst for preparing olefin and coproducing aromatic hydrocarbon by hydrocarbon catalytic cracking and application thereof, wherein a molecular sieve catalyst with 0.45-0.7nm of pore diameter modified by phosphorus, alkaline earth metal, lithium and rare earth is adopted to properly promote aromatization reaction in catalytic cracking reaction of naphtha, gasoline, diesel oil and other fractions, and coproduces aromatic hydrocarbon while producing olefin (the yield of ethylene, propylene and aromatic hydrocarbon is 60-80%).

CN1370216A discloses a synthetic polymer prepared from C ₄₊ A process for preparing light olefin from naphtha by catalytic reaction features that the ZSM-5 molecular sieve and ZSM-11 molecular sieve containing P are prepared from the inert matrix materials such as silicon oxide and argil, and the hydrogen transfer reaction in the water vapour environment is reduced to a maximum extent ₄ ～C ₁₂ The straight run and cracked naphtha material of olefin or alkane is directly converted into light olefin of ethylene, propylene and the like and aromatic hydrocarbon of toluene, xylene and the like which are more valuable.

CN100509714C adopts silicon modified catalyst for C ₄ Catalytic conversion of olefinsThe reaction for producing ethylene, propylene and aromatic hydrocarbon can obtain higher yield of ethylene and propylene, and the content of paraxylene in the produced aromatic hydrocarbon is higher.

The above-mentioned route for producing aromatic hydrocarbon and light olefin simultaneously by using light hydrocarbon as raw material mostly depends on the light hydrocarbon aromatization technical platform, and benefits from the mild operation condition of the relative catalytic cracking process, and the light hydrocarbon aromatization has the outstanding advantages of low coke yield, small processing loss, etc., but the current research mainly focuses on fixed bed catalyst and process stage, and has the problems of low yield of light olefin, serious carbon deposition of catalyst and rapid deactivation.

Disclosure of Invention

The invention aims to solve the problems of low yield of low-carbon olefin, serious carbon deposition of a catalyst, rapid inactivation of the catalyst, poor regeneration stability of the catalyst and the like in the existing light hydrocarbon processing process, and provides a catalyst for processing light hydrocarbon, a preparation method and a regeneration method thereof, and a method for processing light hydrocarbon.

In order to achieve the above object, a first aspect of the present invention provides a catalyst for processing light hydrocarbons, the catalyst comprising a composite carrier, and sulfate and an active component supported on the composite carrier, the active component comprising a rare earth element and/or a group VA element;

the composite support contains 10-50wt% of a hydrogen-type ZSM-5 zeolite, 5-40wt% of zirconia, and 10-85wt% of alumina, based on the total weight of the composite support.

The second aspect of the present invention provides a method for preparing a catalyst for processing light hydrocarbons, the method comprising the steps of:

(1) Preparing composite powder containing hydrogen type ZSM-5 zeolite and zirconium hydroxide by adopting a coprecipitation method;

(2) Mixing the composite powder with alumina sol to obtain slurry; carrying out dropping ball forming on the slurry in an oil ammonia column, drying the obtained wet ball to obtain a dry ball, soaking the dry ball in a sulfuric acid solution, and then drying and roasting to obtain a sulfate radical loaded composite carrier;

(3) And (2) dipping the composite carrier into a solution containing a soluble rare earth compound and/or a soluble VA group element compound, and then drying and roasting to obtain a sulfate radical and active component supported catalyst.

In a third aspect, the present invention provides a process for regenerating a catalyst for processing a light hydrocarbon, the process comprising: in the presence of inert gas, regenerating the deactivated catalyst and oxygen-containing gas to obtain a regenerated catalyst; wherein the deactivated catalyst is a catalyst for continuous reaction for 120h, and the catalyst is the catalyst provided by the first aspect, or the catalyst prepared by the method provided by the second aspect.

In a fourth aspect, the invention provides a method for processing a light hydrocarbon, the method comprising: in the presence of non-hydrogen gas, light hydrocarbon is contacted with a catalyst and reacts; the catalyst is the catalyst provided by the first aspect, or the catalyst prepared by the method provided by the second aspect.

Compared with the prior art, the invention has the following advantages:

(1) The catalyst provided by the invention comprises a composite carrier and sulfate radicals and active components loaded on the composite carrier, and the catalytic activity of the catalyst can be effectively improved by limiting the specific component with specific content in the composite carrier and combining the sulfate radicals and the active components, especially, the content of the active components is further limited, and the catalytic activity of the catalyst is further improved; meanwhile, the catalyst provided by the invention has higher catalytic stability and regeneration performance;

(2) The preparation method of the catalyst provided by the invention has simple process and is convenient for industrial production;

(3) The catalyst provided by the invention is used for processing light hydrocarbon, especially light naphtha, can produce aromatic hydrocarbon and byproduct low-carbon olefin, and obtains higher aromatic hydrocarbon yield and low-carbon olefin yield; meanwhile, the catalyst has strong carbon deposition resistance and long one-way reaction period.

Drawings

FIG. 1 shows the hydrogen form of ZSM-5 zeolite (SiO) of example 1 ₂ /Al ₂ O ₃ Molar ratio of 150) and composite carrier A1, wherein a is hydrogen type ZSM-5 zeolite (SiO) ₂ /Al ₂ O ₃ Molar ratio of 150), b is a TEM image of composite support A1;

FIG. 2 is a graph showing pore size distributions of catalysts (S1 to S4, S9 to S10 and DS 1) obtained in examples 1 to 4, examples 9 to 10 and comparative example 1.

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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.

The invention provides a catalyst for processing light hydrocarbon, which comprises a composite carrier, sulfate radical and an active component, wherein the sulfate radical and the active component are loaded on the composite carrier, and the active component comprises rare earth elements and/or VA group elements;

the composite support contains 10-50wt% of a hydrogen type ZSM-5 zeolite, 5-40wt% of zirconia, and 10-85wt% of alumina, based on the total weight of the composite support.

The inventor of the invention researches and finds that: the catalyst provided by the invention can effectively improve the catalytic activity of the catalyst by limiting the specific component and the specific content of the composite carrier and combining the specific content of the active component, and the catalyst is used for processing light hydrocarbons, especially for aromatization reaction of light naphtha, so that higher aromatic hydrocarbon yield and lower carbon olefin yield can be obtained at the same time, the carbon deposition resistance of the catalyst is improved, and the one-way reaction period of the catalyst is prolonged.

Specifically, the hydrogen type ZSM-5 zeolite in the composite carrier has strong acidity, so that a light naphtha component can be activated into carbonium ions, part of the hydrogen type ZSM-5 zeolite is continuously converted into an aromatic hydrocarbon component, and part of the aromatic hydrocarbon component is converted into ethylene and propylene, and particularly, the hydrogen type ZSM-5 zeolite is subjected to modification treatment (namely weak base multi-stage hole treatment), so that the proportion of mesopores and micropores is obviously improved under the condition that the zeolite keeps intact crystalline phase and stable structure, the contact property of the acid position of the zeolite is greatly improved, the conversion rate of the light naphtha component is increased, the diffusion efficiency of low-carbon olefins is improved, the zeolite can be quickly separated from a reaction system after being generated, secondary reactions such as hydrogen transfer and the like are reduced, and the yield of the low-carbon olefins is obviously increased; the zirconia in the composite carrier forms a rich mesoporous structure on the surface of the hydrogen type ZSM-5 zeolite, so that the diffusion of reactants and products is accelerated, the occurrence of bimolecular reactions consuming low-carbon olefin, such as hydrogen transfer and the like, is further inhibited, and the selectivity of the low-carbon olefin is further improved; the rare earth elements in the active components are beneficial to dehydrogenation and activation of low-carbon alkane molecules in the initial stage of reaction; the VA group element in the active component can effectively reduce the carbon deposit of the catalyst, prolong the one-way reaction time of the catalyst, and improve the regeneration performance, thereby prolonging the service life of the catalyst.

In some embodiments of the present invention, preferably, the composite support contains 20 to 50wt% of the hydrogen ZSM-5 zeolite, 10 to 40wt% of zirconia, and 10 to 70wt% of alumina, based on the total weight of the composite support; further preferably, the composite support contains 20 to 50wt% of the hydrogen type ZSM-5 zeolite, 10 to 40wt% of zirconia, and 40 to 50wt% of alumina, based on the total weight of the composite support. The optimal conditions are adopted, so that the structural fit between two main components of the composite carrier is improved, a mesoporous structure is formed, the ratio of mesopores and micropores is obviously improved, and the performance of the catalyst is obviously improved.

In some embodiments of the invention, it is preferred that the hydrogen form of the ZSM-5 zeolite is SiO ₂ /Al ₂ O ₃ The molar ratio is 100-300:1, e.g., 100: 1.

in some embodiments of the invention, it is preferred that the hydrogen form of the ZSM-5 zeolite has an overall specific surface area of 300 to 480m ² Per g, preferably from 350 to 440m ² (ii)/g; the mesoporous specific surface area is 20-35m ² A/g, preferably from 20 to 30m ² (ii) in terms of/g. With the preferred conditions thatIt is favorable for improving the accessibility of the acid sites of the hydrogen type ZSM-5 zeolite, thereby improving the conversion rate of light hydrocarbon (especially light naphtha) components and the yield of low-carbon olefins.

In the present invention, the specific surface area parameter is measured by the method of ASTM D4365, unless otherwise specified.

In some embodiments of the present invention, preferably, the crystalline form of the alumina is selected from α -Al ₂ O ₃ 、β-Al ₂ O ₃ And gamma-Al ₂ O ₃ Preferably gamma-Al ₂ O ₃ 。

In some embodiments of the present invention, it is preferred that the sulfate content, as S, is from 0.1 to 15wt%, e.g., 0.1wt%, 1wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, and any value in the range of any two numerical compositions, preferably from 1 to 12wt%, based on the total weight of the composite support.

In the present invention, the active component including the rare earth element and/or the VA element means that the active component may contain the rare earth element or the VA element, or both the rare earth element and the VA element, without specific description.

In some embodiments of the present invention, it is preferred that the rare earth element content on an elemental basis is 0.1 to 5wt%, based on the total weight of the composite support, e.g., 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 4wt%, 5wt%, and any value in the range of any two numerical compositions, preferably 0.1 to 3wt%; the group VA element content on an oxide basis is 0.1 to 10wt%, for example, 0.1wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, and any value in the range of any two values is preferably 1 to 8wt%. In the invention, the service life of the catalyst is prolonged by regulating and controlling the contents of the rare earth element and the VA group element, so that the yield of the aromatic hydrocarbon and the yield of the low-carbon olefin are increased.

In some embodiments of the present invention, preferably, the rare earth element is selected from lanthanum and/or cerium, preferably lanthanum, although the present invention is not limited thereto.

In some embodiments of the present invention, preferably, the group VA element is selected from phosphorus and/or antimony, preferably phosphorus, although the present invention is not limited thereto.

In the present invention, there is a wide range of choices for the light hydrocarbon. Preferably, the light hydrocarbon is C ₄ -C ₇ Preferably contains C ₄ -C ₇ The light naphtha of (1). In the present invention, the light naphtha is C ₄ -C ₇ A mixture of lower hydrocarbons of (a); the source of the light naphtha is not limited in the present invention.

According to the present invention, preferably, the particle size of the composite carrier is 1.2 to 2.5mm, for example, 1.2mm, 1.4mm, 1.6mm, 1.8mm, 2mm, 2.2mm, 2.5mm, and any value in the range of any two numerical values, preferably 1.4 to 2.2mm.

In some embodiments of the present invention, preferably, the shape of the composite carrier is spherical, and the diameter of the composite carrier is 1.2 to 2.5mm, preferably 1.4 to 2.2mm.

According to the invention, the total specific surface area of the catalyst is preferably 280 to 450m ² A ratio of per gram, preferably 350 to 440m ² (ii)/g; the mesoporous specific surface area is 40-200m ² A/g, preferably from 40 to 150m ² (ii)/g; the pore volume of the mesopore is 0.1-0.5cm ³ In g, preferably 0.1 to 0.15cm ³ (ii)/g; the most probable pore diameter is 26 to 50nm, preferably 26 to 32nm.

In the present invention, the particle diameter parameter is measured by the method of ASTM D4513-11 without specific description; the mesoporous volume parameter is measured by adopting ASTM D4365; the mode of the most probable pore diameter is measured by ASTM D4641-17.

According to a particularly preferred embodiment of the present invention, a catalyst for processing light naphtha, the catalyst comprising a composite support, and sulfate and an active component supported on the composite support, the active component comprising a rare earth element and a group VA element;

the composite support comprises 20-50wt% of hydrogen type ZSM-5 zeolite, 10-40wt% of zirconia, 40-50wt% of alumina, based on the total weight of the composite support;

based on the total weight of the composite carrier, the sulfate radical content calculated by S is 1-12wt%, the rare earth element content calculated by simple substance is 0.1-3wt%, and the VA group element content calculated by oxide is 1-8wt%.

In a second aspect, the present invention provides a method for preparing a catalyst for processing light hydrocarbons, the method comprising the steps of:

In the present invention, the soluble compound means that the compound is easily soluble in water or, under the action of an auxiliary, easily soluble in water without specific description.

In some embodiments of the present invention, preferably, in step (1), the composite powder is prepared by the following method: mixing the hydrogen type ZSM-5 zeolite and a soluble zirconium compound solution, dropwise adding ammonia water into the mixed solution until the pH value of the solution is 7-10, and then filtering and drying; wherein, the drying condition is preferably 30-120 ℃ and the time is 2-6h.

In some embodiments of the present invention, preferably, the weight ratio of the hydrogen-form ZSM-5 zeolite to the soluble zirconium compound solution is 1:0.1-10, e.g., 1: 1:1, 1:2, 1:3, 1:4, 1:5, 1:8, 1:0.2 to 5, wherein the soluble zirconium compound solution is based on the soluble zirconium compound.

In some embodiments of the present invention, preferably, the concentration of the soluble zirconium compound in the soluble zirconium compound solution is 1 to 50wt%, for example, 1wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 30wt%, 40wt%, 50wt%, and any value in the range of any two values, preferably 2 to 40wt%.

In the present invention, there is a wide range of choices for the kind of the soluble zirconium compound, including but not limited to zirconium oxychloride, zirconium nitrate, and preferably zirconium oxychloride.

In the present invention, the ammonia precipitates a soluble zirconium compound (zirconium oxychloride) to form zirconium hydroxide. Preferably, the ammonia concentration in the aqueous ammonia is from 2 to 15wt%, e.g., 2wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 15wt%, and any value in the range of any two numerical compositions, preferably from 4 to 10wt%.

In some embodiments of the present invention, preferably, the alumina content of the aluminum sol is 8 to 16wt%, e.g., 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 14wt%, 16wt%, and any value in the range of any two numerical compositions is preferably 8 to 12wt%. In the invention, the content of the alumina in the alumina sol is crucial to the dropping ball forming effect of the alumina sol, a spherical carrier cannot be obtained if the content is too low, and the spherical carrier cannot flow and complete the dropping ball forming process if the content is too high.

In the present invention, there is a wide range of choices for the source of the aluminum sol, as long as the content of alumina in the aluminum sol satisfies the above-mentioned definition. Preferably, the aluminum sol is obtained by peptizing an aluminum source and an acid solution.

In some embodiments of the present invention, preferably, the weight ratio of the aluminum source to the acid solution is 1:0.02-0.2, e.g., 1:0.04-0.12, wherein the aluminum source is calculated by alumina.

In the present invention, there is a wide selection range for the aluminum source. Preferably, the aluminum source includes, but is not limited to, pseudoboehmite, an aluminum sol, and preferably, pseudoboehmite.

In some embodiments of the invention, it is preferred that the acid concentration in the acid solution is 0.1 to 5wt%, e.g., 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 3wt%, 4wt%, 5wt%, and any value in the range of any two values, preferably 0.5 to 2wt%.

In the present invention, there is a wide selection range for the acid. Preferably, the acid is selected from inorganic acids and/or organic acids, the inorganic acids preferably being selected from nitric acid and/or hydrochloric acid, more preferably nitric acid; the organic acid is selected from acetic acid and/or formic acid, more preferably acetic acid.

In some embodiments of the invention, preferably, the peptization time is 1 to 10 hours, preferably 2 to 6 hours.

In some embodiments of the present invention, preferably, in step (2), the slurry has a solids content of 18 to 30wt%, for example, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 30wt%, and any value in the range of any two values, preferably 18 to 26wt%; wherein, the solid content refers to the sum of the contents of the hydrogen type ZSM-5 molecular sieve, the zirconium hydroxide and the alumina.

In some embodiments of the present invention, preferably, the weight ratio of the composite powder to the aluminum sol is 1:2-10, e.g., 1: 2. 1:5, 1:6, 1:7, 1:8, 1, and any two numerical ranges, preferably 1:5-8.

In the present invention, the slurry is subjected to dropping-ball forming in an oil ammonia column. Preferably, the oil phase in the oil ammonia column is kerosene, wherein the kerosene is preferably C ₁₀ -C ₁₆ The alkane of (1); the concentration of the aqueous ammonia phase is preferably 5 to 8 wt.%; the dropping bulb temperature is preferably 10 to 30 ℃.

In some embodiments of the present invention, preferably, the slurry is put into an oil ammonia column for drop-ball forming, the temperature of drop-ball forming is 10-30 ℃, and the wet ball is taken out from the ammonia water phase, and dried for 8-24h at 50-80 ℃ to obtain dry ball.

In the invention, the dry ball is immersed in the sulfuric acid solution, and the dry ball can absorb sulfate radicals in the sulfuric acid solution to be connected with zirconia in the composite carrier by a specific acting force to form an effective active component.

In some embodiments of the present invention, preferably, the concentration of sulfuric acid in the sulfuric acid solution is 0.1 to 10wt%, preferably 0.2 to 6wt%.

In some embodiments of the present invention, preferably, the weight ratio of the dry spheres to the sulfuric acid solution is 1:0.5-1.2, preferably 1:0.5-0.8; further preferably, the impregnation time of the dry balls and the sulfuric acid solution is preferably 2-6h, the impregnated product is dried at 90-120 ℃ for 4-20h, and then the dried product is roasted at 500-800 ℃ for 2-8h to obtain the composite carrier, wherein the particle size of the composite carrier is 1.2-2.5mm, preferably 1.4-2.2mm.

In the present invention, the solution containing the soluble rare earth compound and/or the soluble group VA element compound means that the solution may contain the soluble rare earth compound or the soluble group VA compound, or may contain both the soluble rare earth compound and the soluble group VA compound.

In some embodiments of the present invention, preferably, in the step (3), the weight ratio of the composite support and the solution containing the soluble rare earth compound and/or the soluble group VA element compound is 1:0.5-1.2, e.g., 1:0.5-1.

In the present invention, in the step (3), the composite carrier and the solution containing the soluble rare earth compound and the soluble group VA element compound are preferably impregnated at 10 to 40 ℃ for 1 to 4 hours, preferably 2 to 3 hours, and the impregnated product is preferably dried at 90 to 120 ℃ for 4 to 20 hours, and then the dried product is preferably calcined at 500 to 600 ℃ for 2 to 8 hours, preferably 4 to 6 hours, to obtain the catalyst.

In some embodiments of the present invention, preferably, in the solution containing the soluble rare earth compound and/or the soluble group VA element compound, the concentration of the soluble rare earth compound is 0.1 to 10wt%, preferably 0.1 to 6wt%; the concentration of the soluble group VA element compound is 1 to 10wt%, preferably 1 to 8wt%. Here, and/or, it means that the solution may contain a soluble rare earth compound or a soluble group VA element compound, or may contain both a soluble rare earth compound and a soluble group VA element compound.

In some embodiments of the present invention, preferably, the soluble rare earth compound is selected from nitrates and/or chlorates of rare earth elements, for example, lanthanum nitrate, lanthanum chlorate, cerium nitrate, cerium chlorate, but the present invention is not limited thereto.

In some embodiments of the present invention, preferably, the soluble group VA element compound includes, but is not limited to, at least one of phosphoric acid, antimony nitrate, and antimony acetate.

In the invention, in order to further improve the pore distribution of the hydrogen type ZSM-5 zeolite in the catalyst, more mesoporous channels are introduced under the condition that the hydrogen type ZSM-5 zeolite keeps the original channel structure unchanged, so that the catalyst provides more contactable acid sites. Preferably, the method further comprises: and carrying out modification treatment on the hydrogen type ZSM-5 zeolite.

In some embodiments of the present invention, preferably, the modifying process comprises:

(a) Carrying out weak base treatment on the hydrogen type ZSM-5 zeolite and a sodium carbonate solution, filtering and drying to obtain modified zeolite;

(b) And (3) carrying out ammonium ion exchange on the modified zeolite and the ammonium salt solution, filtering, drying and roasting to obtain the multi-stage Kong Qingxing ZSM-5 zeolite.

In the invention, in the step (a), the hydrogen type ZSM-5 zeolite is subjected to weak base treatment by using a sodium carbonate solution so that the treated zeolite has hierarchical pores, and is dried for 2-8h at 90-120 ℃ after being washed by water, so as to obtain the modified zeolite.

In some embodiments of the invention, preferably, the conditions of the weak base treatment and ammonium ion exchange each independently comprise: the temperature is 50-100 ℃, preferably 60-90 ℃; the time is 1 to 10 hours, preferably 4 to 6 hours; the rotation speed is 200-800rpm, preferably 300-600rpm.

In some embodiments of the present invention, preferably, in step (a), the weight ratio of the hydrogen-form ZSM-5 zeolite to the sodium carbonate solution is 1:0.1 to 10, for example, 1.1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:2-5.

In some embodiments of the invention it is further preferred that the concentration of sodium carbonate in the sodium carbonate solution is between 0.05 and 20wt%, preferably between 0.1 and 10wt%.

In the invention, in the step (b), the modified zeolite is subjected to amine ion exchange, and then is dried and calcined to be converted into the multi-stage Kong Qingxing ZSM-5 zeolite, wherein the drying temperature is preferably 90-120 ℃, and the drying time is preferably 2-8h; the calcination temperature is preferably 500-600 deg.C, and the calcination time is preferably 2-10h.

In the present invention, na ions are completely removed from ZSM-5 zeolite. Preferably, the number of ammonium ion exchanges is not less than 1, preferably 2 to 3.

In some embodiments of the present invention, preferably, the weight ratio of the modified zeolite to the ammonium salt solution is 1:3-20, e.g., 1:3, 1:5, 1:8, 1:5-15.

In some embodiments of the invention, it is further preferred that the concentration of ammonium salt in the ammonium salt solution is 0.05 to 10wt%, preferably 0.05 to 5wt%.

In the present invention, there is a wide range of choices for the kind of the ammonium salt as long as the ammonium salt can be hydrolyzed into ammonium ions. Preferably, the ammonium salt is selected from ammonium chloride and/or ammonium nitrate.

In some embodiments of the invention, preferably the multistage Kong Qingxing ZSM-5 zeolite has an overall specific surface area of 300-480m ² Per g, preferably from 350 to 440m ² (iv) g; the specific surface area of the mesoporous is 36-200m ² A/g, preferably of 40 to 100m ² /g。

In the present invention, there is a wide range of choices for the conditions of the regeneration. Preferably, the conditions of the regeneration include: the temperature is 450-550 ℃, preferably 460-520 ℃; the pressure is 0.1-3MPa, preferably 0.5-2MPa; the time is 5-40h, preferably 8-20h.

In some embodiments of the present invention, it is preferred that the volume ratio of the oxygen-containing gas and deactivated catalyst is from 250 to 1000:1, preferably 500 to 1000:1.

in some embodiments of the present invention, preferably, the oxygen-containing gas is a mixed gas of oxygen and an inert gas, and the oxygen-containing gas has an oxygen content of 0.5 to 5 vol%, preferably 0.5 to 2 vol%. In the present invention, the inert gas includes, but is not limited to, nitrogen, helium, argon, neon, and preferably nitrogen, unless otherwise specified.

The catalyst provided by the invention is used for processing light hydrocarbon (especially light naphtha) to convert the light hydrocarbon to generate aromatic hydrocarbon and low-carbon olefin under a non-hydrogenation condition, namely, the light naphtha generates a series of reactions such as cracking, hydrogen transfer, aromatization and the like under the action of the catalyst to generate a liquid product containing the aromatic hydrocarbon, and meanwhile, a byproduct part of liquefied gas component rich in propylene and a dry gas component rich in ethylene are generated.

By adopting the method for processing light hydrocarbon provided by the invention, the light hydrocarbon (especially light naphtha) does not need to be pre-refined; meanwhile, a moving bed reactor and a fixed bed reactor can be adopted for reaction, and the moving bed reactor is preferably adopted, so that the stable and continuous reaction can be ensured; in order to avoid frequent reactor switching due to catalyst regeneration, it is preferred to carry out the reaction using a moving bed apparatus having a plurality of reactors.

In some embodiments of the present invention, preferably, the reaction conditions include: the temperature is 400-650 ℃, preferably 450-600 ℃, and more preferably 520-600 ℃; the pressure is 0.01-2MPa, preferably 0.02-1MPa, more preferably 0.02-0.3MPa; the mass space velocity is 0.01-10h ^-1 Preferably 0.05 to 5h ^-1 Preferably 0.1 to 2h ^-1 。

In some embodiments of the present invention, it is preferred that the volume ratio of the non-hydrogen gas to the light hydrocarbon is from 200 to 1000:1, preferably 400 to 1000:1, more preferably 500 to 800:1. further preferably, the non-hydrogen gas includes, but is not limited to, N ₂ 、CO。

In the present invention, the kind of the light hydrocarbon is defined as above, and the present invention is not described herein.

The present invention will be described in detail below by way of examples.

The specific surface area parameter and the mesoporous pore volume parameter are measured by adopting an ASTM D4365 method; the instrument is as follows: an AsAp2400 static nitrogen adsorber from Micromeritics; the testing process comprises the following steps: the catalyst sample was degassed at 300 ℃ for 4h to a vacuum of 1.33X 10 ^-2 Pa, then contacting nitrogen with the adsorbent to be detected at the liquid nitrogen temperature (-196 ℃), statically achieving adsorption balance, calculating the amount of nitrogen adsorbed by the adsorbent according to the difference value between the nitrogen gas inflow and the amount of nitrogen remained in the gas phase after adsorption, then calculating the specific surface area and the pore volume by using a two-parameter BET formula, and calculating the pore size distribution and the corresponding mesoporous pore volume by using a BJH formula.

Particle size parameters were measured using ASTM D4513-11;

the most probable pore diameter parameter was determined using ASTM D4641-17.

The compositions of the composite supports and catalysts obtained in examples 1 to 12 and comparative examples 1 to 3 are shown in Table 1, and the physical property parameters of the composite supports and catalysts are shown in Table 2.

Example 1

(1) Preparation of multistage Kong Qingxing ZSM-5 zeolite

(a) Weak base ofProcessing: 100g of hydrogen type ZSM-5 zeolite (SiO) ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 350m ² (g) the mesoporous specific surface area is 25m ² Per g) and 1000g of Na with a concentration of 2 wt.% ₂ CO ₃ The aqueous solution is subjected to weak base treatment, and the conditions of the weak base treatment comprise: the temperature is 90 ℃, the time is 4 hours, the rotating speed is 500rpm, the filtration is carried out, the obtained solid is washed by deionized water until the washing liquid is neutral, and the modified zeolite is obtained after drying for 5 hours at the temperature of 110 ℃;

(b) Ammonium ion exchange: 100g of the modified zeolite were each admixed with 1000g of NH having a concentration of 5% by weight ₄ Ammonium ion exchange is carried out on Cl aqueous solution twice, the solid obtained after ion exchange is dried for 5h at 110 ℃, and roasted for 5h at 550 ℃ to obtain the multi-stage Kong Qingxing ZSM-5 zeolite (SiO) ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 400m ² (g) the mesoporous specific surface area is 45m ² /g)。

(2) Preparation of composite powder

52g of zirconium oxychloride (ZrOCl) ₂ ·8H ₂ O, analytically pure) was dissolved in 500g of deionized water to form a clear aqueous solution, and 40g of the above-mentioned multistage Kong Qingxing ZSM-5 zeolite (SiO) was added thereto with stirring ₂ /Al ₂ O ₃ The molar ratio is 150), uniformly stirring, dripping ammonia water with the concentration of 6wt% until the pH value is 8, filtering, washing the obtained solid with water, and drying at 110 ℃ for 4 hours to obtain the composite powder.

(3) Preparation of composite Carrier

Taking 32g pseudo-boehmite (A), (B) and (C)

SB powder with an alumina content of 75 wt%), adding 190g of 1.1wt% nitric acid aqueous solution under stirring, and peptizing for 2h to obtain alumina sol with an alumina content of 11 wt%; adding 36g of the composite powder, and stirring at a high speed of 120rpm for 3 hours to obtain slurry containing zeolite and zirconium hydroxide, wherein the solid content in the slurry is 24wt%;

dropping the slurry into an oil ammonia column to form a dropping ball, wherein the dropping ball temperature is 15 ℃, the oil phase in the oil ammonia column is kerosene, the thickness of the oil phase is 10cm, the thickness of the ammonia water phase is 200cm, and the concentration of the ammonia water is 6wt%; taking out the wet balls from the bottom of the ammonia water layer, drying at 60 ℃ for 10h, soaking the obtained dry balls in a 4.9wt% sulfuric acid solution for 4h (the liquid/solid weight ratio is 1:1), drying at 110 ℃ for 4h, and roasting at 700 ℃ for 3h to obtain a composite carrier A1;

the TEM image of the composite carrier A1 is shown in fig. 1, and as can be seen from fig. 1, compared with ZSM-5 zeolite, zirconia in the composite carrier forms a rich mesoporous structure on the surface of hydrogen-type ZSM-5 zeolite, so that the diffusion of reactants and products is accelerated, the bimolecular reactions consuming low-carbon olefins, such as hydrogen transfer, are further suppressed, the selectivity of the low-carbon olefins is improved, and the reaction effect is significantly improved.

(4) Preparation of the catalyst

30g of the composite carrier A1 was impregnated with 30g of a solution containing 3wt% lanthanum chloride and 6wt% phosphoric acid at 25 ℃ for 2 hours, and the impregnated solid was dried at 110 ℃ for 4 hours and calcined at 550 ℃ for 4 hours to obtain a catalyst S1.

The pore distribution graph of the catalyst S1 is shown in fig. 2, and it can be seen from fig. 2 that the catalyst S1 has an obvious mesoporous structure after the multi-stage pore treatment.

Example 2

The procedure is as in example 1, except that, in step (2), 52g of zirconium oxychloride (ZrOCl) ₂ ·8H ₂ O, analytically pure) was replaced by 26g of zirconium oxychloride (ZrOCl) ₂ ·8H ₂ O, analytical pure); 40g of the above multistage Kong Qingxing ZSM-5 zeolite (SiO) was added ₂ /Al ₂ O ₃ 150 molar ratio) was replaced with 50g of the multistage Kong Qingxing ZSM-5 zeolite (SiO) ₂ /Al ₂ O ₃ The molar ratio is 150) to obtain composite powder; the other conditions are the same, and the composite carrier A2 and the catalyst S2 are obtained.

The pore distribution curve of the catalyst S2 is shown in fig. 2, and it can be seen from fig. 2 that the specific surface area and pore volume of the mesopores of the catalyst S2 are increased due to the increased zeolite content of the multi-stage Kong Qingxing ZSM-5 compared to the catalyst S1.

Example 3

Following the procedure of example 1, exceptIn the step (2), 52g of zirconium oxychloride (ZrOCl) ₂ ·8H ₂ O, analytically pure) was dissolved in 500g of deionized water and replaced with 105g of zirconium oxychloride (ZrOCl) ₂ ·8H ₂ O, analytically pure) was dissolved in 300g of deionized water, and 40g of the above multistage Kong Qingxing ZSM-5 zeolite (SiO) ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 400m ² (g) the mesoporous specific surface area is 45m ² Per g) was replaced with 20g of the multistage Kong Qingxing ZSM-5 zeolite (SiO) described above ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 400m ² (g) the mesoporous specific surface area is 45m ² And/g) to obtain composite powder, and obtaining the composite carrier A3 and the catalyst S3 under the same conditions.

The pore distribution curve of the catalyst S3 is shown in fig. 2, and it can be seen from fig. 2 that the specific surface area and pore volume of the mesopores of the catalyst S3 are reduced due to the reduced zeolite content of the multi-stage Kong Qingxing ZSM-5 compared to the catalyst S1.

Example 4

A catalyst S4 was obtained by following the procedure of example 1 except that in the step (3), 36g of the composite powder was replaced with 24g of the composite powder to obtain a composite carrier A4, and the remaining conditions were the same.

The pore distribution curve of the catalyst S4 is shown in fig. 2, and it can be seen from fig. 2 that, compared with the catalyst S1, the catalyst S4 has a reduced content of the composite powder, so that the proportion of the multi-stage Kong Qingxing ZSM-5 zeolite in the catalyst S4 is reduced, and the specific surface area and the pore volume of the mesopores are reduced.

Example 5

The same procedure was followed as in example 1, except that in step (4), 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 6% by weight was replaced with 30g of a solution containing lanthanum chloride at a concentration of 1.5% by weight and phosphoric acid at a concentration of 6% by weight, and the remaining conditions were changed, to obtain catalyst S5.

Example 6

The same procedure as in example 1 was conducted except that in step (4), 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 6% by weight was replaced with 30g of a solution containing cerium chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 6% by weight, and the remaining conditions were changed, to obtain catalyst S6.

Example 7

The same procedure as in example 1 was conducted except that in step (4), 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 6% by weight was replaced with 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 12% by weight, and the remaining conditions were changed, to obtain catalyst S7.

Example 8

The same procedure was followed as in example 1, except that in step (4), 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 6% by weight was replaced with 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and antimony nitrate at a concentration of 5% by weight, and the remaining conditions were changed to obtain catalyst S8.

Example 9

The procedure is as in example 1, except that, in step (1 a), 100g of ZSM-5 zeolite in hydrogen form (SiO) ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 350m ² Per gram, the mesoporous specific surface area is 25m ² Per g) to 100g of hydrogen ZSM-5 zeolite (SiO ₂ /Al ₂ O ₃ The molar ratio is 200, and the total specific surface area is 350m ² (g) the mesoporous specific surface area is 25m ² And/g) under the same conditions, to obtain a composite carrier A9 and a catalyst S9.

The pore distribution curve of catalyst S9 is shown in fig. 2, and it can be seen from fig. 2 that catalyst S9 prepared from ZSM-5 zeolite having a higher silica/alumina ratio has a slightly lower mesopore pore volume than catalyst S1.

Example 10

The procedure is as in example 1, except that, in step (1 a), 1000g of Na having a concentration of 2% by weight are added ₂ CO ₃ The aqueous solution was replaced with 1000g of 5wt% Na ₂ CO ₃ And obtaining the composite carrier A10 and the catalyst S10 by using the aqueous solution under the same conditions.

The pore distribution curve of the catalyst S10 is shown in FIG. 2, and it can be seen from FIG. 2 that Na is used at a relatively high concentration ₂ CO ₃ After the aqueous solution treatment, mesopores with larger size and wider range appear on the catalyst S10.

Example 11

The procedure of example 1 was followed, except that, without step (1), 40g of hydrogen-form ZSM-5 zeolite (SiO) were directly charged ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 350m ² (g) the mesoporous specific surface area is 25m ² /g) was added to the clear solution, and the conditions were the same to obtain a composite carrier A11 and a catalyst S11.

The pore distribution curve of the catalyst S11 is shown in fig. 2, and it can be seen from fig. 2 that the catalyst S11 without modification treatment (hierarchical pore treatment) has no mesoporous structure and mainly has microporous pores.

Example 12

The same procedures as in example 1 were repeated except that, in step (4), 30g of a solution containing lanthanum chloride at a concentration of 3% by weight and phosphoric acid at a concentration of 6% by weight was replaced with 30g of a solution containing lanthanum chloride at a concentration of 3% by weight, thereby obtaining catalyst S12.

Comparative example 1

(1) Preparation of the support

Taking 67.6g of pseudoboehmite (A), (B), (C)

SB powder with the alumina content of 75 wt%), adding 380g of 1.1wt% nitric acid aqueous solution under stirring, and peptizing for 2h to obtain alumina sol with the alumina content of 11 wt%; 50g of hydrogen type ZSM-5 zeolite (SiO) was added thereto ₂ /Al ₂ O ₃ The molar ratio is 150, and the total specific surface area is 350m ² Per gram, the mesoporous specific surface area is 25m ² (g) stirring at a high speed of 120rpm for 3h to obtain a slurry containing zeolite and zeolite, wherein the solid content in the slurry is 20wt%;

dropping the slurry into an oil-ammonia column to form a dropping ball, wherein the temperature of the dropping ball is 15 ℃, the oil phase in the oil-ammonia column is kerosene, the thickness of the oil-ammonia column is 10cm, the thickness of the ammonia water phase is 200cm, and the concentration of the ammonia water is 6wt%; taking out the wet ball from the bottom of the ammonia water layer, drying at 60 ℃ for 10h, and activating at 550 ℃ for 3h to obtain a composite carrier DA1;

(2) Preparation of the catalyst

50g of the composite carrier DA1 was impregnated with 50g of a solution containing 3wt% lanthanum chloride and 6wt% phosphoric acid at 25 ℃ for 2 hours, and the impregnated solid was dried at 110 ℃ for 4 hours and calcined at 550 ℃ for 4 hours to obtain a catalyst DS1.

The pore distribution curve of the catalyst DS1 is shown in fig. 2, and it can be seen from fig. 2 that the catalyst DS1 subjected to the multi-stage pore treatment has no mesoporous structure and mainly has microporous pore channels.

Comparative example 2

(1) Preparation of zirconia powder

Dissolving 150g of zirconium oxychloride in 800g of deionized water to form a clear aqueous solution, dripping ammonia water until the pH value is 8.0, filtering, washing the obtained solid with water, and drying at 110 ℃ for 4 hours to obtain zirconium hydroxide powder.

(2) Preparation of composite Carrier

67.6g of pseudo-boehmite are taken (a)

SB powder with an alumina content of 75 wt%), adding 380g of 1.1wt% nitric acid aqueous solution under stirring, and peptizing for 2h to obtain alumina sol with an alumina content of 11 mass%; adding 50g of the zirconium hydroxide powder into the slurry, and stirring the mixture at a high speed of 120rpm for 3 hours to obtain slurry containing zirconium hydroxide, wherein the solid content in the slurry is 20wt%;

dropping the slurry into an oil ammonia column to form a dropping ball, wherein the dropping ball temperature is 15 ℃, the oil phase of the oil ammonia column is kerosene, the thickness of the oil ammonia column is 10cm, the thickness of the ammonia water phase is 200cm, and the concentration of the ammonia water is 6wt%; and taking out the wet balls from the bottom of the ammonia water layer, drying the wet balls at 60 ℃ for 10h, soaking the obtained dry balls in a 4.9wt% sulfuric acid solution for 4h (the liquid/solid mass ratio is 1:1), drying the wet balls at 110 ℃ for 4h, and roasting the wet balls at 700 ℃ for 3h to obtain the composite carrier DA2.

(3) Preparation of the catalyst

50g of the composite carrier DA2 was impregnated with 50g of a mixed solution containing 3wt% lanthanum chloride and 6wt% phosphoric acid at 25 ℃ for 2 hours, and the impregnated solid was dried at 110 ℃ for 4 hours and calcined at 550 ℃ for 4 hours to obtain the catalyst DS2.

Comparative example 3

The procedure of example 1 was followed, except that in the step (3), the dry pellets were directly dried and calcined to obtain a composite support DA3, and the rest of the procedure was the same, to obtain a catalyst DS3.

TABLE 1

Note: * Based on the total weight of the composite carrier; * SiO in hydrogen type ZSM-5 zeolite ₂ /Al ₂ O ₃ The molar ratio.

TABLE 2

As can be seen from the data in Table 2, the catalyst provided by the invention has a relatively obvious mesoporous structure, and the specific surface area and the pore volume of mesopores are both higher than those of a comparative example.

Test example 1

The catalysts (S1 to S12 and DS1 to DS 3) obtained in examples 1 to 12 and comparative examples 1 to 3 were subjected to a catalytic performance test.

And (3) testing conditions: the catalysts (S1 to S12 and DS1 to DS 3) obtained in examples 1 to 12 and comparative examples 1 to 3 were packed in small fixed bed reactors, respectively, and light naphtha having a composition shown in Table 3 was introduced into the reactors as a raw material, contacted with the catalyst and reacted under reaction conditions including: the temperature is 590 ℃, the pressure is 0.1MPa, and the mass space velocity is 0.5h ^-1 The time was 24 hours, the volume ratio of nitrogen to light naphtha was 800, and the reaction results are shown in Table 4.

TABLE 3

TABLE 4

Note: dry gas is H ₂ 、CH ₄ And C ₂ A hydrocarbon.

TABLE 4

Note: the dry gas is H ₂ 、CH ₄ And C ₂ A hydrocarbon.

As can be seen from the data in Table 4, compared with comparative examples 1-3, the catalyst provided by the invention can be used for processing light hydrocarbon, and can simultaneously obtain higher aromatic hydrocarbon yield and lower carbon olefin yield.

Test example 2

The catalyst S1 obtained in example 1 was subjected to a stability test.

And (3) testing conditions are as follows: a small fixed bed reactor was packed with the catalyst S1 obtained in example 1, and a light naphtha having a composition shown in Table 3 was introduced as a raw material into the reactor, and the catalyst S1 was brought into contact with the light naphtha and reacted under reaction conditions including: the temperature is 590 ℃, the pressure is 0.1MPa, and the mass space velocity is 0.5h ^-1 The reaction time was 120 hours, the volume ratio of nitrogen to light naphtha was 800, and the reaction results are shown in Table 5.

TABLE 5

Continuous reaction time, h	24	48	72	96	120
						Yield of dry gas, wt%	38.4	37.5	36.5	35.2	34.5
(C ₃ +C ₄ ) Yield, wt.%	31.0	31.3	32.1	32.6	32.7
						C ₅₊ Yield, wt.%	30.6	31.2	31.4	32.2	32.8
Ethylene yield, wt.%	19.3	18.8	18.7	18.3	17.9
						Yield of propylene, wt.%	21.1	21.5	21.3	20.9	20.7
Yield of light olefins, wt%	40.4	40.3	40.0	39.2	38.6
						Aromatic yield, wt.%	27.2	26.8	26.2	25.6	25.3

Note: the dry gas is H ₂ 、CH ₄ And C ₂ A hydrocarbon.

As can be seen from the data in Table 5, the yield of aromatics decreases from 27.2wt% at 24h to 25.3wt% at 120h with the increase of reaction time, and the average yield of aromatics is higher than 26wt%; the yield of the low-carbon olefin is reduced from 40.4wt% in the continuous reaction for 24 hours to 38.6wt% in the continuous reaction for 120 hours, and the average yield of the low-carbon olefin is more than 39wt%, namely, the catalyst provided by the invention has good aromatization activity, selectivity of aromatic hydrocarbon and low-carbon olefin and reaction stability.

Test example 3

The catalyst S1 obtained in example 1 was subjected to a regeneration test.

And (3) testing conditions are as follows: a small fixed bed reactor was packed with the catalyst S1 obtained in example 1, and a light naphtha having a composition shown in Table 3 was introduced into the reactor as a raw material, and the reaction was carried out in contact with the catalyst S1 under reaction conditions including: the temperature is 590 ℃, the pressure is 0.1MPa, and the mass space velocity is 0.5h ^-1 The time is 120h, the volume ratio of nitrogen to light naphtha is 800, and the reaction is continuously carried outThe catalyst S1 was regenerated as deactivated catalyst for 120 h.

The regeneration method comprises the following steps: introducing oxygen-containing gas with the oxygen content of 1 volume percent into a reactor bed layer for regeneration, wherein the regeneration conditions comprise that: the temperature is 450 ℃, the pressure is 0.5MPa, and the mass space velocity is 0.5h ^-1 The time was 10 hours, the volume ratio of the oxygen-containing gas to the deactivated catalyst was 500, to obtain a regenerated catalyst, and the regenerated catalyst was reused for the reaction for 120 hours, and the reaction results are shown in Table 6.

TABLE 6

Number of times of catalyst regeneration	0	1
			Dry gas yield, wt%	34.5	34.2
(C ₃ +C ₄ ) Yield, wt.%	32.7	32.6
			C ₅₊ Yield, wt.%	32.8	33.2
Ethylene yield, wt.%	17.9	17.6
			Yield of propylene, wt.%	20.7	21.0
Yield of light olefins, wt%	38.6	38.6
			Aromatic yield, wt.%	25.3	25.1

Note: dry gas is H ₂ 、CH ₄ And C ₂ A hydrocarbon.

As can be seen from the data in Table 6, after the catalyst S1 provided in example 1 is regenerated, the catalytic activity is very close to the activity before regeneration, which shows that the catalyst provided by the invention has very good regeneration performance.

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

1. A catalyst for processing light hydrocarbon is characterized by comprising a composite carrier, sulfate radical and an active component, wherein the sulfate radical and the active component are loaded on the composite carrier, and the active component comprises rare earth elements and/or VA group elements;

2. The catalyst of claim 1, wherein the composite support contains 20-50wt% of a hydrogen ZSM-5 zeolite, 10-40wt% of zirconia, and 10-70wt% of alumina, based on the total weight of the composite support;

and/or, in the hydrogen type ZSM-5 zeolite, siO ₂ /Al ₂ O ₃ The molar ratio is 100-300:1, preferably 120 to 250:1;

and/or the total specific surface area of the hydrogen type ZSM-5 zeolite is 300-480m ² A ratio of per gram, preferably 350 to 440m ² (iv) g; the mesoporous specific surface area is 20-35m ² A/g, preferably from 20 to 30m ² /g；

And/or the crystal form of the alumina is selected from alpha-Al ₂ O ₃ 、β-Al ₂ O ₃ And gamma-Al ₂ O ₃ Preferably gamma-Al ₂ O ₃ 。

3. Catalyst according to claim 1 or 2, wherein the sulfate content in S is 0.1-15wt%, preferably 1-12wt%, based on the total weight of the composite support.

4. A catalyst according to any one of claims 1 to 3, wherein the rare earth element is present in an amount of 0.1 to 5wt%, preferably 0.1 to 3wt%, calculated as simple substance, based on the total weight of the composite support; the content of group VA elements in terms of oxide is 0.1-10wt%, preferably 1-8wt%;

and/or the rare earth element is selected from lanthanum and/or cerium;

and/or the group VA elements are selected from phosphorus and/or antimony;

and/or the light hydrocarbon is C ₄ -C ₇ Preferably contains C ₄ -C ₇ The light naphtha of (1).

5. The catalyst according to any one of claims 1 to 4, wherein the particle size of the composite support is 1.2-2.5mm, preferably 1.4-2.2mm;

and/or the total specific surface area of the catalyst is 280-450m ² Per g, preferably from 350 to 440m ² (ii)/g; the mesoporous specific surface area is 40-200m ² A ratio of/g, preferably 40 to 150m ² (ii)/g; the pore volume of the mesoporous is 0.1-0.5cm ³ The preferred range is 0.1 to 0.15 cm/g ³ (iv) g; the most probable pore diameter is 26 to 50nm, preferably 26 to 32nm.

6. A preparation method of a catalyst for processing light hydrocarbon is characterized by comprising the following steps:

7. The method according to claim 6, wherein in the step (1), the composite powder is prepared by the following method: mixing the hydrogen type ZSM-5 zeolite and a soluble zirconium compound solution, dropwise adding ammonia water into the mixed solution until the pH value of the solution is 7-10, and then filtering and drying;

preferably, the weight ratio of the hydrogen-form ZSM-5 zeolite to the soluble zirconium compound solution is 1:0.1 to 10, preferably 1:0.2 to 5, wherein the soluble zirconium compound solution is based on the soluble zirconium compound;

preferably, the concentration of the soluble zirconium compound in the soluble zirconium compound solution is 1 to 50wt%, preferably 2 to 40wt%.

8. The method according to claim 6 or 7, wherein in step (2), the alumina content in the aluminum sol is 8-16wt%, preferably 8-12wt%;

and/or the aluminum sol is obtained by peptizing an aluminum source and an acid solution;

preferably, the weight ratio of the aluminum source to the acid solution is 1:0.02 to 0.2, preferably 1:0.04 to 0.12, wherein the aluminum source is calculated as alumina;

preferably, the acid concentration in the acid liquor is 0.1-5wt%, preferably 0.5-2wt%;

preferably, the peptization time is 1-10h, preferably 2-6h.

9. The process according to any one of claims 6 to 8, wherein in step (2), the slurry has a solids content of 18 to 30wt%, preferably 18 to 26wt%;

and/or the weight ratio of the composite powder to the aluminum sol is 1:2-10, preferably 1:5-8;

and/or, the concentration of the sulfuric acid in the sulfuric acid solution is 0.1-10wt%, preferably 0.2-6wt%;

and/or the weight ratio of the dry balls to the sulfuric acid solution is 1:0.5-1.2, preferably 1:0.5-0.8.

10. The method according to any one of claims 6 to 9, wherein in the step (3), the weight ratio of the composite support and the solution containing the soluble rare earth compound and/or the soluble group VA element compound is 1:0.5-1.2, preferably 1:0.5 to 1;

and/or, in the solution containing the soluble rare earth compound and/or the soluble group VA element compound, the concentration of the soluble rare earth compound is 0.1-10wt%, and preferably 0.1-6wt%; the concentration of the soluble group VA element compound is 1-10wt%, and preferably 1-8wt%;

and/or, the soluble rare earth compound is selected from nitrates and/or chlorates of rare earth elements;

and/or the soluble group VA element compound is selected from at least one of phosphoric acid, antimony nitrate and antimony acetate.

11. The method of any one of claims 6-10, wherein the method further comprises: modifying the hydrogen type ZSM-5 zeolite;

preferably, the process of the modification treatment comprises:

(b) Carrying out ammonium ion exchange on the modified zeolite and the ammonium salt solution, filtering, drying and roasting to obtain the multi-stage Kong Qingxing ZSM-5 zeolite;

preferably, the multi-stage Kong Qingxing ZSM-5 zeolite has a total specific surface area of 300-480m ² Per g, preferably from 350 to 440m ² (iv) g; the specific surface area of the mesoporous is 36-200m ² A/g, preferably of 40 to 100m ² /g；

Preferably, the conditions of the weak base treatment and ammonium ion exchange each independently comprise: the temperature is 50-100 ℃, preferably 60-90 ℃; the time is 1 to 10 hours, preferably 4 to 6 hours; the rotating speed is 200-800rpm, preferably 300-600rpm;

preferably, the weight ratio of the hydrogen-form ZSM-5 zeolite to the sodium carbonate solution is 1:0.1 to 10, preferably 1:5-10;

preferably, the weight ratio of the modified zeolite to the ammonium salt solution is 1:3-20, preferably 1:5-15.

12. A process for regenerating a catalyst for processing light hydrocarbons, the process comprising: in the presence of inert gas, regenerating the deactivated catalyst and oxygen-containing gas to obtain a regenerated catalyst;

wherein the deactivated catalyst is a catalyst for continuous reaction for 120h, and the catalyst is the catalyst of any one of claims 1 to 5, or the catalyst prepared by the method of any one of claims 6 to 11.

13. The method of claim 12, wherein the conditions of regeneration comprise: the temperature is 450-550 ℃, preferably 460-520 ℃; the pressure is 0.1-3MPa, preferably 0.5-2MPa; the time is 5 to 40 hours, preferably 8 to 20 hours;

and/or the volume ratio of the oxygen-containing gas to the deactivated catalyst is 250-1000:1, preferably 500 to 1000:1;

and/or the oxygen-containing gas is a mixed gas of oxygen and inert gas, and the oxygen content in the oxygen-containing gas is 0.5-5 vol%, preferably 0.5-2 vol%.

14. A method for processing a light hydrocarbon, the method comprising: in the presence of non-hydrogen gas, light hydrocarbon is contacted with a catalyst and reacts;

wherein the catalyst is the catalyst of any one of claims 1 to 5 or the catalyst prepared by the method of any one of claims 6 to 11.

15. The method of claim 14, wherein the conditions of the reaction comprise: the temperature is 400-650 ℃, preferably 450-600 ℃, and more preferably 520-600 ℃; the pressure is 0.01-2MPa, preferably 0.02-1MPa, more preferably 0.02-0.3MPa; the mass space velocity is 0.01-10h ^-1 Preferably 0.05 to 5h ^-1 Preferably 0.1 to 2h ^-1 (ii) a The time is 90 to 240 hours, preferably 120 to 180 hours;

and/or the volume ratio of the non-hydrogen gas to the light hydrocarbon is 200-1000:1, preferably 400 to 1000:1, more preferably 500 to 800:1;

and/or, the light hydrocarbon is C ₄ -C ₇ Preferably contains C ₄ -C ₇ The light naphtha of (1).