CN114075453A

CN114075453A - Catalytic cracking gasoline hydro-upgrading method

Info

Publication number: CN114075453A
Application number: CN202010826724.7A
Authority: CN
Inventors: 向永生; 王廷海; 王高峰; 姚文君; 李景锋; 高海波; 常晓昕; 张永泽; 尹玲玲; 鲍晓军
Original assignee: Petrochina Co Ltd; Fuzhou University
Current assignee: Petrochina Co Ltd; Fuzhou University
Priority date: 2020-08-17
Filing date: 2020-08-17
Publication date: 2022-02-22
Anticipated expiration: 2040-08-17
Also published as: CN114075453B

Abstract

The invention relates to a catalytic cracking gasoline hydrogenation modification method, firstly, under the action of a pre-hydrogenation catalyst, whole fraction catalytic cracking gasoline passes through a pre-hydrogenation reactor to remove dialkene, mercaptan and thioether, then, under the action of hydrodesulfurization and isomerization catalysts, the pre-hydrogenation product is subjected to selective hydrodesulfurization, and simultaneously linear chain olefin is isomerized into single-branch olefin or single-branch paraffin to obtain clean gasoline with ultra-low sulfur content; the pre-hydrogenation catalyst takes one or more of amorphous silicon-aluminum, alumina, a Y molecular sieve and ZSM-5 as a carrier, and is impregnated with one or more active components of cobalt, molybdenum and nickel. The catalytic cracking gasoline hydro-upgrading method is used for producing clean gasoline with ultralow sulfur and low octane value loss.

Description

Catalytic cracking gasoline hydro-upgrading method

Technical Field

The invention relates to the field of catalytic cracking gasoline hydrogenation, in particular to a catalytic cracking gasoline hydrogenation modification method.

Background

At present, the catalytic gasoline hydrodesulfurization catalyst pays more attention to keeping octane number not lost while achieving the purposes of desulfurization and olefin reduction. CN107151563A provides a clean gasoline production method coupling ultra-deep desulfurization and olefin high-octane number conversion. The production method comprises the following steps: contacting full fraction gasoline with a sulfur transfer catalyst under a hydrogen condition to generate a directional low-temperature sulfur transfer reaction, and then cutting oil products to obtain light fraction gasoline and heavy fraction gasoline; mixing light fraction gasoline with organic acid, and carrying out esterification reaction on C5-C7 olefin in the mixture under the action of an esterification catalyst; the heavy fraction gasoline and the selective hydrodesulfurization catalyst and the supplementary desulfurization-hydrocarbon isomerization catalyst respectively undergo selective hydrodesulfurization reaction and hydrocarbon isomerization reaction; the treated light fraction steamThe oil is mixed with the treated heavy fraction gasoline to obtain the ultra-low sulfur high octane gasoline. The production method provided by the invention is suitable for treating inferior gasoline, especially high-sulfur high-olefin catalytic cracking gasoline, and can maintain or improve the octane number of the gasoline while carrying out ultra-deep desulfurization. CN101508913A relates to a hydro-upgrading method for deep desulfurization and octane number recovery of full-range poor gasoline. The inferior full-range gasoline is in contact reaction with three different catalysts in three-stage reaction zones, the reaction temperature of the first stage is lower, and a high-selectivity hydrodesulfurization catalyst is adopted to remove sulfur compounds which are difficult to remove and minimize olefin saturation; the second stage reaction temperature is higher, and a supplementary desulfurization-hydrocarbon single branched chain isomerization/aromatization catalyst is adopted to realize the complete removal of sulfur compounds and further reduce the olefin content; the third stage has relatively low reaction temperature, and adopts hydrocarbon multi-branched chain hydroisomerization catalyst to perform multi-branched chain isomerization on the residual olefin and straight-chain paraffin, so as to improve the octane number of the product. The invention can obtain good hydro-upgrading effect especially for middle-sulfur and high-olefin poor quality catalytic cracking gasoline, can maintain or improve the product octane number and keep higher product liquid yield while greatly reducing the contents of olefin and sulfur, and can produce national IV and even higher standard clean gasoline. CN109647442A discloses a fully-sulfurized hydrorefining catalyst and a preparation method thereof. The catalyst comprises MoS with the mass of the catalyst as 100 percent₂20.3-26.1％，NiS₂5.8-7.4 percent of alumina, and the balance of alumina; the specific surface area of the catalyst is 250-450 m²The pore volume is 0.4-0.6 mL/g. The catalyst is a completely vulcanized catalyst, does not need to be vulcanized or activated, has high hydrodesulfurization and denitrification activities, and can be used as a hydrofining catalyst.

The alumina carrier is widely used in the fields of heterogeneous catalysts, catalyst carriers and the like, and the thermal stability, hydrothermal stability, coking resistance and the like of the carrier alumina are not ideal. Usually, an auxiliary agent is added for modification to improve the carrier performance. There are many patents and technologies of modified alumina carriers, and CN101898131A discloses a dehydrogenation catalyst using Sn-containing alumina as a carrier and a preparation method thereof, wherein the dehydrogenation catalyst uses Sn-containing alumina as a carrier, carbon nanofibers are loaded on the surfaces of pore channels of the carrier, and a dehydrogenation active metal component is loaded by an impregnation method. The preparation method of the catalyst comprises the following steps: introducing Sn into a carrier when alumina is gelatinized, loading carbon nanofibers on the Sn-containing alumina carrier in situ through ethylene cracking, then soaking dehydrogenation active components, and carrying out heat treatment and steam treatment to obtain the final dehydrogenation catalyst. The catalyst of the present invention is used in the dehydrogenation of hydrocarbon, especially propane, and has high activity, high selectivity and high stability. The most commonly used carrier of the gasoline hydrodesulfurization catalyst is alumina, and in order to improve the activity and stability of the catalyst, the composite carrier is prepared by using modified alumina such as silicon, titanium, magnesium, boron, phosphorus and the like, so that the pore structure and surface acidity of the catalyst and the interaction between active components and the carrier can be adjusted. In addition, the specific surface area of the carrier is increased by modulating the pore structure of the carrier, and the performance of the carrier is more than several times better than that of the similar product used at present.

Disclosure of Invention

The invention provides a method for hydro-upgrading catalytic gasoline, in particular to a method for producing clean gasoline with ultralow sulfur content and small octane value loss through pre-hydrogenation, hydrodesulfurization and isomerization processes of the catalytic gasoline.

Therefore, the invention provides a catalytic gasoline hydro-upgrading method, which comprises the following steps:

(1) pre-hydrogenating the full-fraction catalytically cracked gasoline under the action of a pre-hydrogenation catalyst to remove diolefin, mercaptan and thioether to obtain a pre-hydrogenated product;

(2) the pre-hydrogenation product is subjected to hydrodesulfurization under the action of hydrodesulfurization and isomerization catalysts, and linear olefins are isomerized into single-branch olefins or single-branch paraffins, so that clean gasoline with ultra-low sulfur content is obtained;

wherein, the pre-hydrogenation catalyst comprises 8-18 wt% of active component and a carrier, and the active component comprises one or more of cobalt, molybdenum and nickel; the carrier comprises one or more of amorphous silicon aluminum, alumina, a Y molecular sieve and ZSM-5;

the hydrodesulfurization and isomerization catalyst comprises a carrier and an active component, the catalyst comprises a MoCoS active phase and/or a NiCoS active phase, and the catalyst contains more than 3 wt% of S.

In the method for hydro-upgrading catalytically cracked gasoline, the carrier in the hydro-desulfurization and isomerization catalyst preferably comprises 70.0-90.0 wt% of Al based on the carrier₂O₃0.5-4.0 wt% of CoSnO₃9.0-35.0 wt% of ZSM-5 molecular sieve containing mesopores-macropores; based on the catalyst, the active component contains 5.0-16.0 wt% of molybdenum, 1.5-6.0 wt% of cobalt and 0.2-4.5 wt% of magnesium in terms of mass of oxides.

In the method for hydro-upgrading catalytically cracked gasoline, the carrier preferably comprises 76.0-84.0 wt% of Al₂O₃，1.5-4.0wt％CoSnO₃9.0-25.0 wt% of ZSM-5 molecular sieve containing mesopores-macropores; the active component contains 8.0-16.0 wt% of molybdenum, 1.5-5.0 wt% of cobalt and 0.2-3.5 wt% of magnesium.

In the method for hydro-upgrading catalytically cracked gasoline, the carrier in the hydro-desulfurization and isomerization catalyst preferably comprises 75.0-87.0 wt% of Al based on the carrier₂O₃1.0-3.0 wt% of CoSnO₃1.0-4.5 wt% of La₂Sn₃O₇9.0-35.0 wt% of ZSM 5 molecular sieve containing mesopores-macropores; based on the catalyst, the active component contains 5.0-16.0 wt% of molybdenum, 1.5-6.0 wt% of cobalt, 2.5-8.5 wt% of nickel and 0.2-4.5 wt% of magnesium in terms of mass of oxides.

In the method for hydro-upgrading catalytically cracked gasoline, the carrier preferably comprises 76.0-85.0 wt% of Al₂O₃，1.5-3.0wt％CoSnO₃，1.5-3.5wt％La₂Sn₃O₇9.0-25.0 wt% of ZSM 5 molecular sieve containing mesopores-macropores; the active component contains 8.0-16.0 wt% of molybdenum, 1.5-5.0 wt% of cobalt and 0.2-3.5 wt% of magnesium.

In the method for hydro-upgrading catalytically cracked gasoline, the CoSnO is preferred₃The preparation method comprises the following steps: separating tin source and cobalt sourceDissolving, mixing and stirring uniformly, adding alkali liquor, reacting for 7-24h at the temperature of 120-180 ℃, cooling, washing and drying the obtained reactant to obtain precursor powder, and calcining the precursor powder at the temperature of 560-800 ℃ for 2-6h to obtain CoSnO₃。

The catalytic cracking gasoline hydro-upgrading method provided by the invention is preferably that the ZSM-5 molecular sieve containing the mesopores and the macropores has the aperture of 2-70 nm and the total specific surface area of 300-350 m²/g、360～400m²(ii)/g or 410 to 450m²/g。

The catalytic cracking gasoline hydro-upgrading method provided by the invention is preferably that the pore volume of the ZSM-5 molecular sieve containing the mesopores and the macropores is 0.20-0.24 m³/g、0.25～0.30m³A/g or 0.31 to 0.35m³/g。

In the method for hydro-upgrading catalytically cracked gasoline according to the present invention, it is preferable that the Co content in the carrier is lower than the amount of Co supported by the catalyst, in terms of the mass of CoO in the hydrodesulfurization and isomerization catalyst.

The method for hydro-upgrading the catalytically cracked gasoline, which is disclosed by the invention, preferably comprises the following steps of:

(1) preparation of slurry I: adding acid solution containing styrene-butadiene rubber emulsion into CoSnO₃In the powder, the adding amount of acid solution containing styrene-butadiene rubber emulsion is CoSnO based on the mass of the styrene-butadiene rubber emulsion₃5-30.0 wt% of the powder, and uniformly mixing to obtain slurry I;

(2) preparation of powder I: adding deionized water into pseudo-boehmite, continuously adding slurry I under the stirring condition, then adding ZSM-5 molecular sieve containing mesopores and macropores, and then carrying out ultrasonic dispersion, suction filtration and drying to obtain the product containing CoSnO₃And a pseudoboehmite powder I;

(3) preparation of the carrier: mixing the powder I with a binder, adding inorganic acid and deionized water for kneading, extruding into strips, drying and roasting to obtain the CoSnO₃The alumina carrier of (1);

(4) preparation of the impregnation liquid: mixing a molybdenum-containing solution, a cobalt-containing solution and a magnesium-containing solution to obtain a mixed solution, adjusting the pH value of the mixed solution to 2-4, and then adding a vulcanizing agent to obtain a dipping solution containing Co, Mo, Mg and S;

(5) preparation of a catalyst precursor: impregnating the carrier with an impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;

(6) preparation of the catalyst: and (3) vulcanizing the catalyst precursor, cooling to room temperature, filtering, washing with deionized water, and then drying in vacuum to obtain the catalyst.

In the method for hydro-upgrading catalytically cracked gasoline, the pH value of the acid solution containing styrene-butadiene rubber emulsion in the step (1) is preferably below 6; in the step (3), the roasting conditions are as follows: 480-700 ℃ for 4-10 hours; in the step (4), the adding amount of the vulcanizing agent in the impregnation liquid is 80-130% of the theoretical sulfur-carrying amount of the catalyst, and is further preferably 90-115%; in the step (6), the vulcanization step is: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr to complete sulfurization; the temperature of the vacuum drying is 80-150 ℃.

The catalytic gasoline hydro-upgrading method of the invention preferably comprises the following steps: refluxing the catalyst precursor at 65-75 deg.c for 0.5-1.5 hr, adding reductant to react at 100-140 deg.c for 2-6 hr and sulfurizing.

(I) preparation of the carrier:

adding acid solution containing styrene-butadiene rubber emulsion into CoSnO₃In the powder, the mass of the styrene-butadiene rubber emulsion is calculated, and the adding amount of acid liquor containing the styrene-butadiene rubber emulsion is CoSnO₃5-30.0 wt% of the powder, and mixing uniformly to obtain slurry (1);

adding sodium polyacrylate and/or ammonium polyacrylate into deionized water, and adding La₂Sn₃O₇The addition amount of sodium polyacrylate and/or ammonium polyacrylate is La₂Sn₃O₇2 to 20 wt% of (a) to obtain a slurry (2);

under the condition of stirring, adding deionized water into 50-70% of pseudo-boehmite, continuously adding 55-80% of slurry (1) under the condition of stirring, then adding 50-80% of ZSM-5 molecular sieve containing mesopores and macropores, then adding 50-60% of slurry (2), finally sequentially adding the rest pseudo-boehmite, the rest slurry (1), the rest ZSM-5 molecular sieve containing mesopores and macropores and the rest slurry (2), and then carrying out ultrasonic dispersion, suction filtration and drying to obtain the product containing CoSnO₃And pseudoboehmite powder;

mixing the powder with a binder, adding inorganic acid and deionized water for kneading, extruding into strips, drying, and roasting at 480-700 ℃ for 4-10 hours to obtain the La-containing powder₂Sn₃O₇、CoSnO₃The alumina carrier of (1);

(II) preparation of catalyst:

mixing a molybdenum-containing solution, a cobalt-containing solution, a nickel-containing solution and a magnesium-containing solution, adjusting the pH value of the mixed solution to 2-4, and dissolving a vulcanizing agent to obtain a dipping solution containing Co, Mo, Ni, Mg and S;

impregnating the carrier with an impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;

and (3) vulcanization process: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr to complete sulfurization;

cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150 deg.C to obtain the final catalyst product.

According to the catalytic cracking gasoline hydro-upgrading method, the addition amount of the vulcanizing agent in the impregnation liquid is preferably 85-120% of the theoretical sulfur carrying amount of the catalyst.

The method for hydro-upgrading the catalytically cracked gasoline comprises the following steps:

(1) adjusting the pH value of the solution containing the active components to 2-4, and then adding a vulcanizing agent to obtain an impregnation liquid;

(2) impregnating the carrier with an impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;

(3) refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr to complete sulfurization;

(4) cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150 deg.C to obtain the final catalyst product.

The catalytic cracking gasoline hydro-upgrading method of the invention is characterized in that the conditions of the pre-hydrogenation treatment are preferably as follows: the reaction temperature is 90-155 ℃, the reaction pressure is 1.5-4.5MPa, and the liquid volume space velocity is 2-7h^-1The volume ratio of hydrogen to oil is 4-7: 1;

the hydrodesulfurization conditions are as follows: the reaction temperature is 220 ℃ and 300 ℃, the reaction pressure is 1.5-4.5MPa, and the volume space velocity is 2.5-5h^-1The volume ratio of hydrogen to oil is 180-400: 1.

The invention provides a catalytic gasoline hydro-upgrading method, which is specifically described as follows:

firstly, removing alkadiene, mercaptan and thioether from full-fraction FCC gasoline by a prehydrogenation reactor under the action of a prehydrogenation catalyst, then carrying out selective hydrodesulfurization on the prehydrogenation product under the action of hydrodesulfurization and isomerization catalysts, and isomerizing straight-chain olefin into single-branch olefin or single-branch paraffin to obtain the clean gasoline with ultra-low sulfur content.

The pre-hydrogenation catalyst takes one or more of amorphous silicon-aluminum, alumina, a Y molecular sieve and ZSM-5 as a carrier and one or more of cobalt, molybdenum and nickel as an active component; the active component accounts for 8-18 wt% of the catalyst. In the active component of the catalyst, molybdenum and cobalt exist in the form of MoCoS, nickel and cobalt exist in the form of NiCoS, and the catalyst contains more than 3 wt% of sulfur, preferably 3-15 wt% of sulfur, and more preferably 3-6 wt% of sulfur.

The preparation method of the pre-hydrogenation catalyst comprises the following steps: mixing one or more of molybdenum-containing solution, cobalt-containing solution and nickel-containing solution, adjusting the pH value of the mixed solution to 2-4, and dissolving a vulcanizing agent such as ammonium sulfide to obtain impregnation liquid containing Co, Mo and/or Ni and S; impregnating the carrier with an impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization process: refluxing the catalyst precursor at 60-80 deg.C for 0.3-2.0 hr, adding reducing agent such as hydrazine hydrate solution accounting for more than 10% of the volume of the catalyst, and continuously reacting at 100-150 deg.C for 0.5-10 hr to finish sulfurization; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150 deg.C to obtain the final catalyst product.

The sulfuration type catalyst has low sulfuration temperature, and avoids the generation of a spinel structure with lower activity by active metal and carrier alumina, thereby improving the reaction activity of the catalyst. Meanwhile, the vulcanization is carried out at low temperature, so that the energy consumption is reduced, and the production cost is saved.

The pre-hydrogenation reaction mainly comprises the steps that under the action of a pre-hydrogenation catalyst, small molecular mercaptan and thioether have a thioetherification reaction (unsaturated for mono-olefin and high selective hydrogenation activity of the catalyst) with diene, double bond isomerization (namely terminal olefin is converted into internal olefin) is carried out, and the rest diene is saturated.

The conditions of the pre-hydrogenation reaction are as follows: the reaction temperature is 90-155 ℃, the reaction pressure is 1.5-4.5MPa, and the liquid volume space velocity is 2-7h^-1The volume ratio of hydrogen to oil is 4-7: 1.

The hydrodesulfurization and isomerization reaction process conditions are as follows: the reaction temperature is 220 ℃ and 300 ℃, the reaction pressure is 1.5-4.5MPa, and the volume space velocity is 2.5-5h^-1The volume ratio of hydrogen to oil is 180-400: 1.

The catalytic gasoline hydrodesulfurization and isomerization catalyst comprises a carrier and an active component, wherein the carrier contains Al₂O₃ZSM-5 molecular sieve containing mesopores and macropores, CoSnO₃The load of cobalt, molybdenum and magnesium is used for producing the clean gasoline with ultra-low sulfur and high octane number.

Furthermore, in the catalytic gasoline hydrodesulfurization and isomerization catalyst, the carrier is taken as the reference, and the carrier comprises 70.0-90.0 wt% of Al₂O₃，0.5-4.0wt％CoSnO₃9.0-35.0 wt% of ZSM-5 molecular sieve containing mesopores-macropores; based on the catalyst, calculated by the mass of oxide, molybdenum in the active component5.0 to 16.0 wt%, 1.5 to 6.0 wt% cobalt, 0.2 to 4.5 wt% magnesium, the molybdenum and cobalt being present in the form of MoCoS in the active component of the catalyst, the catalyst containing more than 3% of sulphur, preferably 3 to 15 wt% of sulphur, more preferably 3 to 6 wt% of sulphur.

Further preferably, the catalyst support comprises 76.0-84.0 wt% Al₂O₃，1.5-4.0wt％CoSnO₃9.0-25.0 wt% of ZSM-5 molecular sieve containing mesopores and macropores, wherein the active component comprises 8.0-16.0 wt% of molybdenum, 1.5-5.0 wt% of cobalt and 0.2-3.5 wt% of magnesium in terms of oxide.

The invention also provides a preparation method of the catalytic gasoline hydrodesulfurization and isomerization catalyst, which comprises the following steps:

(I) preparation of the carrier: adding acid solution containing styrene-butadiene rubber emulsion into CoSnO₃In the powder, the adding amount of acid solution containing styrene-butadiene rubber emulsion is CoSnO according to the mass of the styrene-butadiene rubber emulsion₃5-30.0 wt% of the powder, and mixing uniformly to obtain slurry (1); adding deionized water into pseudo-boehmite, continuously adding the slurry (1) under the stirring condition, adding a ZSM-5 molecular sieve containing mesopores and macropores, and performing ultrasonic dispersion, suction filtration and drying to obtain a product containing CoSnO₃And a powder of pseudoboehmite; mixing the powder with a binder such as sesbania powder, adding an inorganic acid such as nitric acid and deionized water for kneading, extruding into strips, drying, and roasting at 480-700 ℃ for 4-10 hours to obtain the CoSnO₃The alumina carrier.

Process for the preparation of the support of the invention, CoSnO₃The carrier has an occupying effect, has a part of through macropores, and has good stability and selectivity.

(II) preparation of catalyst:

mixing a molybdenum-containing solution, a cobalt-containing solution and a magnesium-containing solution, adjusting the pH value of the mixed solution to 2-4, and then dissolving a vulcanizing agent such as ammonium sulfide to obtain a dipping solution containing Co, Mo, Mg and S; impregnating CoSnO with impregnating solution₃Aging the alumina carrier for more than 4 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization process: catalyst precursorRefluxing at 60-80 deg.C for 0.3-2.0 hr, adding hydrazine hydrate solution as reductant, and reacting at 100-150 deg.C for 0.5-10 hr to complete sulfurization; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150 deg.C to obtain the final catalyst product.

Because the source of the gasoline is diversified and deteriorated, the contents of colloid, sulfur, arsenic and other impurities in the gasoline have obvious influence on the activity of the catalyst, even the catalyst bed layer does not have obvious temperature rise, and the catalyst is inactivated. In order to improve the impurity resistance of the catalyst and further improve the catalyst, the invention also provides another gasoline hydrodesulfurization and isomerization catalyst, which comprises a carrier and an active component, wherein the carrier comprises 75.0-87.0 wt% of Al based on the carrier₂O₃，1.0-3.0wt％CoSnO₃，1.0-4.5wt％,La₂Sn₃O₇9.0-35.0 wt% of a ZSM 5 molecular sieve containing meso-macropores, the active components being, calculated as oxides, 5.0-16.0 wt% molybdenum, 1.5-6.0 wt% cobalt, 2.5-8.5 wt% nickel, 0.2-4.5 wt% magnesium, the catalyst comprising a MoCoS active phase and a NiCoS active phase, the catalyst containing more than 3% sulphur, preferably 3-15 wt% sulphur, more preferably 3-8 wt% sulphur.

Further preferably, the catalyst support comprises 76.0-85.0 wt% Al₂O₃，1.5-4.0wt％CoSnO₃，1.5-3.5wt％La₂Sn₃O₇9.0-25.0 wt% of ZSM 5 molecular sieve containing mesopores and macropores; the active component contains 8.0-16.0 wt% of molybdenum, 1.5-5.0 wt% of cobalt and 0.2-3.5 wt% of magnesium.

The invention also provides a preparation method of the other gasoline hydrodesulfurization and isomerization catalyst, which comprises the following steps:

(I) preparation of the carrier:

adding acid solution containing styrene-butadiene rubber emulsion into CoSnO₃In the powder, the adding amount of acid liquor containing the styrene-butadiene rubber emulsion is CoSnO based on the mass of the styrene-butadiene rubber emulsion₃5-30.0 wt% of the powder, and mixing uniformly to obtain slurry (1);

sodium polyacrylate and/or ammonium polyacrylate(the addition amount is La)₂Sn₃O₇2-20 wt%) was added to deionized water, followed by addition of La₂Sn₃O₇To obtain La-containing₂Sn₃O₇A slurry (2);

under the condition of stirring, adding deionized water into 50-70% of pseudo-boehmite, continuously adding 55-80% of slurry (1) under the condition of stirring, then adding 50-80% of ZSM-5 molecular sieve containing mesopores and macropores, then adding 50-60% of slurry (2), finally sequentially adding the rest of pseudo-boehmite, the rest of slurry (1), the rest of ZSM-5 molecular sieve containing mesopores and macropores and the rest of slurry (2), and then carrying out ultrasonic dispersion, suction filtration and drying to obtain the product containing La₂Sn₃O₇Powder of CoSnO3 and pseudo-boehmite;

mixing the powder with a binder sesbania powder, adding an inorganic acid such as nitric acid and deionized water for kneading, extruding into strips, drying, and roasting at 480-700 ℃ for 4-10 hours to obtain the La-containing powder₂Sn₃O₇、CoSnO₃The alumina carrier.

Preparation method of the Carrier of the invention La₂Sn₃O₇、CoSnO₃The carrier not only has an occupying effect, but also has a part of through macropores, so that the carrier has good stability and selectivity, and can adjust the phase structure of the alumina and the acidity and alkalinity of the surface of the carrier to form a proper La-Sn-Al proportion, thereby reducing the binding force of the alumina carrier and a metal active component in a high-temperature phase forming process, and further improving the dispersibility of the active metal on the surface of the carrier. Effectively inhibits colloid, arsenic, lead and other impurities from being adsorbed on the surface of the catalyst, covers the center of an active site and improves the impurity resistance of the catalyst. The cobalt molybdenum nickel catalyst prepared by the carrier is particularly beneficial to forming a CoMoS active phase, reducing the consumption of active metals and improving the desulfurization activity of the hydrogenation catalyst. The preparation method of the catalyst carrier of the invention, pseudo-boehmite and CoSnO₃Slurry (1), ZSM-5 molecular sieve containing mesoporous macropores, and La₂Sn₃O₇The slurry (2) is added in two times, which is helpful for improving the anti-coking performance of the carrier and the strength of the carrier, and the surface of the prepared cobalt-molybdenum-nickel catalyst is alive due to the coverage of colloidThe activity is reduced due to the neutral site center, and the activity of the regenerated catalyst can be recovered.

(II) preparation of catalyst:

mixing a molybdenum-containing solution, a cobalt-containing solution, a nickel-containing solution and a magnesium-containing solution, adjusting the pH value of the mixed solution to 2-4, and then dissolving a vulcanizing agent such as ammonium sulfide to obtain a dipping solution containing Co, Mo, Ni, Mg and S; impregnating the carrier with an impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization process: refluxing the catalyst precursor at 60-80 deg.C for 0.3-2.0 hr, adding reducing agent such as sodium sulfide solution, and reacting under heating conditions of 100-150 deg.C for 0.5-10 hr to complete sulfurization; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150 deg.C to obtain the final catalyst product.

In the present invention, La₂Sn₃O₇The preparation of (A) is not limited, and for example, it can be prepared as follows: mixing lanthanum-containing salt solution with sodium stannate, adjusting the pH value of the alkali liquor to 10.5-12, aging, filtering, washing, drying, roasting at 800-950 ℃ to obtain La₂Sn₃O₇。

Further preferably, the vulcanization process: refluxing the catalyst precursor at 65-75 deg.C for 0.5-1.5 hr, adding reducing agent such as hydrazine hydrate solution accounting for more than 10% of the volume of the catalyst, and continuously reacting at 100-140 deg.C for 2-6 hr to finish sulfurization. Among them, the amount of the reducing agent to be added is more preferably 20 to 70% by volume, most preferably 20 to 50% by volume, based on the catalyst.

In the present invention, CoSnO₃The preparation method of (3) is not limited, and a conventional preparation method can be adopted. The CoSnO₃Can be prepared according to the following method: respectively dissolving a tin source and a cobalt source, mixing and stirring uniformly, adding alkali liquor, reacting for 7-24h at the temperature of 120-180 ℃, cooling, washing and drying the obtained reactant to obtain precursor powder. Calcining the precursor powder at 560 ℃ and 800 ℃ for 2-6h to obtain CoSnO₃. The invention uses 0.5-4.0 wt% of CoSnO₃The catalyst is introduced into an alumina carrier, and then a sulfurized cobalt-molybdenum hydrodesulfurization catalyst is prepared, so that the growth of supported cobalt grains is effectively controlled, the aggregation of the cobalt grains is inhibited, and the MoCoS activity is promotedThe formation of the sexual phase is beneficial to improving the desulfurization activity of the catalyst.

Further improved, control CoSnO in alumina carrier₃Such that the amount of Co (all in terms of CoO) in the alumina support is less than the amount of Co supported by the catalyst.

Of course, the inevitable production of MoCoS active phase, MoS, in the catalyst of the invention₂、CoS₂And even molybdenum oxide and cobalt oxide exist. In order to form MoCoS active phase with high activity as much as possible, the invention introduces CoSnO instead of directly introducing oxides such as cobalt, tin and the like₃The method is introduced into an alumina carrier, and then the sulfide type cobalt-molybdenum hydrodesulfurization-isomerization catalyst is prepared, so that the growth of supported cobalt grains is effectively controlled, the aggregation of the cobalt grains is inhibited, the formation of a MoCoS active phase is promoted, and the desulfurization activity of the catalyst is favorably improved. The content of Co in the alumina carrier is lower than the amount of Co loaded by the catalyst in terms of oxide, which is beneficial to improving the dispersity of active components on the surface of the carrier and improving the utilization rate of the active components, and the catalyst has good stability.

The mesoporous-macroporous ZSM-5 molecular sieve is preferably a molecular sieve of CN 110510632A. The carrier of the invention simultaneously contains alumina and CoSnO₃And the ZSM-5 molecular sieve containing the mesopores and the macropores can promote the isomerization reaction of terminal straight chain, especially single straight chain paraffin hydrocarbon, while hydrodesulfurizing.

The pore diameter of the ZSM-5 molecular sieve containing the mesopores and the macropores is 2-70 nm, and the total specific surface area is 300-350 m²The volume of the particles is 360-400 m²G, or 410 to 450m²(ii) a range of/g.

The pore volume of the ZSM-5 molecular sieve containing the mesopores and the macropores is 0.20-0.24 m³A/g or 0.25 to 0.30m³A/g, further alternatively 0.31 to 0.35m³(ii) a range of/g. The content of macropores is controlled to be 3-45% of the total pores, and the content of mesopores is controlled to be 5-65% of the total pores. Adjusting CoSnO according to raw material properties and product control indexes₃Adjusting the content and the content of the styrene-butadiene rubber emulsion, and adjusting the pore structure.

The preparation method of the ZSM-5 molecular sieve containing the mesopores and the macropores is preferably carried out according to the following steps: silicon source, aluminum source, inorganic acid or inorganic base,Deionized water is prepared into mixture gel, and the molar ratio of each component calculated by oxide is 1.0SiO₂:0.00025～0.5Al₂O₃:10～80H₂Adjusting the pH value of the mixture to 9.5-13.0, and then stirring and refluxing the mixture for 2-48 h at the temperature of 60-100 ℃ in a container; and (2) adding the rubber microemulsion into the gel refluxed in the step (1) according to the proportion (R) of the dry basis mass of the rubber microemulsion to the mass of the silicon element in the silicon source of 0.5-50, crystallizing at 150-200 ℃ for 12-72 h, filtering and washing the synthesized product, drying at 80-140 ℃ for 2-12 h, and roasting at 500-600 ℃ for 4-10 h to obtain the mesoporous-macroporous ZSM-5 molecular sieve.

The gasoline hydrodesulfurization and isomerization catalyst carrier comprises Al₂O₃，CoSnO₃，La₂Sn₃O₇ZSM-5 molecular sieve containing mesopore-macropore, and loaded active components of molybdenum, cobalt, nickel and magnesium. The sulfuration type cobalt-molybdenum series hydrodesulfurization and isomerization catalyst is prepared by low-temperature vulcanization, which is beneficial to modulating the hydrodesulfurization, isomerization and hydrodehydrogenation activities of the catalyst and inhibiting an olefin saturation activity center, and the catalyst has low olefin saturation activity, high hydrodesulfurization-isomerization activity and low octane number loss. The catalyst is used for producing clean gasoline meeting the national fifth and sixth standards by catalytic cracking gasoline.

Detailed Description

The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.

The raw material reagents used in the invention are all commercial products.

Example 1

Preparation of Pre-hydrogenation catalyst

111g of alumina and 12.0g of sesbania powder are added into a kneader and mixed evenly, then nitric acid, 260g of ZSM-5 and deionized water are added for kneading evenly, and the mixture is kneaded and extruded to form strips. Drying at 130 ℃ for 9 hours, and roasting at 550 ℃ for 6 hours to obtain a carrier, wherein the carrier comprises the following components: 70 percent of ZSM-5 and 30 percent of alumina.

The preparation method of the pre-hydrogenation catalyst comprises the following steps: preparing impregnation liquid of molybdenum, cobalt and nickel according to the proportion of 7 wt% of molybdenum oxide, 1.5 wt% of cobalt oxide and 3.6 wt% of nickel oxide in the catalyst, mixing the molybdenum-containing solution, the cobalt-nickel solution, adjusting the pH value of the mixed solution to 2.6, and dissolving ammonium sulfide to obtain the impregnation liquid containing Co, Mo, Ni and S; soaking a carrier in soaking liquid containing Co, Mo, Ni and S, and aging for 5 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanizing the catalyst: adding the catalyst precursor into a flask with reflux, refluxing for 1.0 hour at 65 ℃, adding 43mL of hydrazine hydrate and 90mL of deionized water, raising the temperature to 110 ℃, continuously refluxing for 4 hours, ending vulcanization, and reducing the temperature to room temperature. Filtering, washing with deionized water, and vacuum drying to obtain the pre-hydrogenation catalyst product.

Preparation of hydrodesulfurization and isomerization catalysts

1. Preparation of mesoporous-macroporous ZSM-5 molecular sieve

Firstly, 40 percent of water glass, aluminum sulfate, sodium hydroxide and deionized water are mixed according to the mole ratio of oxides of 1SiO₂:0.02Al₂O₃:0.55Na₂O:62.4H₂And adding O into a crystallization kettle, refluxing and stirring for 24h at 80 ℃, adding the rubber microemulsion into the mixture gel according to the proportion of R2.5 before crystallization, then filtering and washing the synthesized product, drying for 6h at 120 ℃ and roasting for 6h at 550 ℃ when crystallizing for 48h at 190 ℃, and obtaining the product 1. The crystallinity is 95%; the aperture of the meso-macroporous is 2-58 nm, and the pore volume is 0.23m³Per g, total specific surface area 304m²(ii)/g; the silicon/aluminum molar ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 48.

2. Preparation of CoSnO₃

22.5g SnCl₄·5H₂O was dissolved in deionized water to give a solution (a), and 22.2g of CoCl was added₂·6H₂Dissolving O in deionized water to obtain solution (b), adding the solution (b) into the solution (a) under stirring, stirring uniformly, adding NaOH solution, stirring uniformly, transferring the obtained mixture into a reaction tank, reacting at 140 ℃ for 11h, and cooling to obtain the final productWashing and drying the reactant to obtain precursor powder. Calcining the precursor powder at 700 ℃ for 3.0h to obtain CoSnO₃。CoSnO₃Grinding for later use.

3. Preparation of the support

An acid solution (pH 6) containing 1.2g of styrene-butadiene rubber emulsion was added to 6.2g of CoSnO₃Uniformly mixing the powder to obtain slurry (1); 245.7g of pseudo-boehmite is added into deionized water, then the slurry (1) is added into the pseudo-boehmite under the stirring condition, then 21.8g of ZSM-5 molecular sieve containing mesopores and macropores is added, and then the mixture is subjected to ultrasonic dispersion, suction filtration and drying to obtain the product containing CoSnO₃And a powder of pseudoboehmite; mixing the powder and sesbania powder, adding nitric acid and deionized water for kneading, extruding, forming, drying, roasting at 540 ℃ for 5.5 hours to obtain the product containing CoSnO₃The alumina carrier 1. The alumina content in the carrier 1 was 86 wt%, CoSnO₃The content is 3.1 wt%, and the ZSM-5 content is 10.9 wt%.

4. Preparation of the catalyst

Preparing an impregnation solution of molybdenum, cobalt and magnesium according to the proportion of 0.3 wt% of molybdenum oxide, 2.1 wt% of cobalt oxide and 1.8 wt% of magnesium oxide in the catalyst, adjusting the pH value of the solution to 2.2 by adopting nitric acid, then adding 32g of ammonium sulfide into the solution, and dissolving to obtain the impregnation solution containing Mo, Co, Mg and S. And (3) spraying and soaking the soaking solution of Co, Mo, Mg and S into the alumina carrier by adopting a normal-temperature equal-volume spraying and soaking method, and aging for 8 hours at room temperature under a closed condition to obtain a catalyst precursor. And (3) a catalyst vulcanization process: adding the catalyst precursor into a flask with reflux, refluxing for 25min at 75 ℃, continuously adding 50mL of hydrazine hydrate and 100mL of deionized water, raising the temperature to 110 ℃, continuously refluxing for 4 hours, finishing vulcanization, and reducing the temperature to room temperature. Filtering, washing with deionized water, and vacuum drying to obtain Co-Mo-S catalyst product 1.

Example 2

1. The preparation process of the mesoporous-macroporous ZSM-5 molecular sieve is the same as that of example 1, except that the mixture ratio is different from that of 1.2SiO₂:0.02Al₂O₃:0.55Na₂O:62.4H₂O, the pore diameter of the meso-macroporous is 2-67 nm, and the pore volume is 0.25m³Per g, total specific surface area of 318m²(ii)/g; the silicon/aluminum molar ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 53. The pH of the acid solution containing styrene butadiene rubber emulsion was 5.5.

2. Preparation of CoSnO₃The procedure of (2) was the same as in example 1.

3. The carrier was prepared in the same manner as in example 1, except that the carrier was composed of 78 wt% of alumina and 3.6 wt% of CoSnO₃8.4 wt% of ZSM-5 molecular sieve containing mesopores and macropores.

4. The procedure for the preparation of the catalyst was the same as in example 1, with the active components of the catalyst being 12.4 wt% molybdenum, 1.6 wt% cobalt and 1.1 wt% magnesium. The amount of ammonium sulfide added was 105% of the theoretical sulfur loading of the catalyst.

Example 3

1. The preparation process of the mesoporous-macroporous ZSM-5 molecular sieve is the same as that of example 1, except that the mixture ratio is different from 0.85SiO₂:0.02Al₂O₃:0.55Na₂O:62.4H₂O, the pore diameter of the meso-macroporous is 2-56 nm, and the pore volume is 0.28m³Per g, total specific surface area of 308m²(ii) in terms of/g. The pH of the acid solution containing the styrene-butadiene rubber emulsion was 5.

2. Preparation of CoSnO₃The procedure of (2) was the same as in example 1.

3. The carrier was prepared in the same manner as in example 1, except that the carrier comprised 89 wt% alumina and 1.4 wt% CoSnO₃9.6 wt% of ZSM-5 molecular sieve containing meso-macropores.

4. The procedure for the preparation of the catalyst was the same as in example 1, except that the catalyst 3 had an active component of 11.3 wt% molybdenum, 3.0 wt% cobalt and 1.3 wt% magnesium. The amount of ammonium sulfide added was 115% of the theoretical sulfur loading of the catalyst.

Example 4

1. The preparation process of the mesoporous-macroporous ZSM-5 molecular sieve is the same as that of example 1, except that the mixture ratio is different from 1.5SiO₂:0.02Al₂O₃:0.55Na₂O:62.4H₂O, the pore diameter of the meso-macroporous is 2-67 nm, and the pore volume is 0.25m³Per g, total specific surface area of 318m²(ii)/g; the silicon/aluminum molar ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 53. The pH of the acid solution containing the styrene-butadiene rubber emulsion was 6.

2. Preparation of CoSnO₃The procedure of (2) was the same as in example 1.

3. The carrier was prepared in the same manner as in example 1, except that the carrier was composed of 81 wt% of alumina and 2.1 wt% of CoSnO₃16.4 wt% of ZSM-5 molecular sieve containing mesopores and macropores.

4. The procedure for the preparation of the catalyst was the same as in example 1, except that the catalyst 4 had an active component containing 9.8 wt% of molybdenum, 4.6 wt% of cobalt and 0.9 wt% of magnesium. The amount of ammonium sulfide added is 100% of the theoretical sulfur loading of the catalyst.

Example 5

Based on the mass of the styrene-butadiene rubber emulsion, the adding amount of the acid solution (pH is 6) containing the styrene-butadiene rubber emulsion is CoSnO₃Preparation of CoSnO containing 16 wt% of the powder₃To obtain a slurry (1);

according to the addition of sodium polyacrylate accounting for CoSnO₃Preparation of La containing 16 wt%₂Sn₃O₇The slurry (2);

under the condition of stirring, adding deionized water into 60% pseudoboehmite, continuously adding 70% slurry (1) under the condition of stirring, then adding 55% of ZSM-5 molecular sieve containing mesopores and macropores in the embodiment 4, then adding 50% slurry (2), finally sequentially adding the rest pseudoboehmite, the rest slurry (1), the rest ZSM-5 molecular sieve containing mesopores and the rest slurry (2), and then carrying out ultrasonic dispersion, suction filtration and drying to obtain the La-containing material₂Sn₃O₇、CoSnO₃And pseudoboehmite powder;

mixing the powder and sesbania powder, adding nitric acid and deionized water for kneading, extruding, molding, drying, and roasting at 650 ℃ for 5 hours to obtain the La-containing powder₂Sn₃O₇、CoSnO₃The alumina carrier.

The alumina content in the carrier 5 was 78 wt%, CoSnO₃Content 1.4 wt%, La₂Sn₃O₇The content is 2.8 wt%, and the content of ZSM-5 molecular sieve containing mesopores and macropores is 17.8 wt%.

Mixing a molybdenum-containing solution, a cobalt-containing solution, a nickel-containing solution and a magnesium-containing solution, adjusting the pH value of the mixed solution to 3, and dissolving ammonium sulfide to obtain a dipping solution containing Co, Mo, Ni, Mg and S; soaking a carrier in soaking liquid containing Co, Mo, Ni, Mg and S, and aging for 5 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization process: refluxing the catalyst precursor at 70 ℃ for 1.5 hours, adding 32g of sodium sulfide solution, continuously reacting at 130 ℃ for 6 hours, and finishing vulcanization; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 120 deg.C to obtain the final catalyst product. The amount of ammonium sulfide added was 125% of the theoretical sulfur loading of the catalyst.

Calculated by the mass of the oxide, the content of molybdenum in the catalyst is 11.7 wt%, the content of cobalt is 2.2 wt%, the content of nickel is 3.1 wt%, and the content of magnesium is 0.5 wt%.

FCC gasoline (sulfur content of 140.3mg/kg, olefin content of 32.7 v%, arsenic content of 114 μ g/kg and gum content of 1.67mg/mL) was first treated by a pre-hydrogenation reactor to remove diolefins, as well as mercaptans, thioethers, while double bond isomerization (i.e., conversion of terminal olefins to internal olefins) and saturation of the remaining diolefins. The reaction temperature is 120 ℃, the reaction pressure is 1.8MPa, and the liquid volume space velocity is 4h^-1The volume ratio of hydrogen to oil is 4: 1. The prehydrogenation product with 100 percent of diene removed is subjected to deep desulfurization and isomerization by a hydrodesulfurization unit under the action of hydrodesulfurization-isomerization catalysts 1-5, and the reaction process conditions are as follows: the temperature of the reactor is 265 ℃, the reaction pressure is 2.0MPa, and the volume space velocity is 3.6h^-1Hydrogen to oil volume ratio 330. A sample was taken after about 60 hours of reaction and analyzed, and the results are shown in Table 1.

TABLE 1 catalyst hydrodesulfurization-isomerization results

As can be seen from Table 1, the hydrodesulfurization and isomerization catalyst reacted at a reactor temperature of 265 ℃ had octane number loss of 0.2 to 0.4 unit, low octane number loss, high liquid yield, high desulfurization rate, good activity, liquid yield of 97.9% or more, and increase of the mono-branched olefin by 10.3% or more and increase of the mono-branched paraffin by 12.3% or more. Further, it is understood from the above that the olefin saturation ratios of the catalysts 1 to 5 obtained in examples were 12.3%, 11.6%, 13.2%, 14.6% and 9.4%, respectively.

The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims

1. A catalytic gasoline hydro-upgrading method is characterized by comprising the following steps:

2. The method of claim 1, wherein the hydrodesulfurization and isomerization catalyst comprises 70.0-90.0 wt.% Al based on the support₂O₃0.5-4.0 wt% of CoSnO₃9.0-35.0 wt% of ZSM-5 molecular sieve containing mesopores-macropores; based on the catalyst, the active component contains 5.0-16.0 wt% of molybdenum, 1.5-6.0 wt% of cobalt and 0.2-4.5 wt% of magnesium in terms of mass of oxides.

3. The process for hydro-upgrading of catalytically cracked gasoline according to claim 2, characterized in that,the carrier comprises 76.0-84.0 wt% of Al₂O₃，1.5-4.0wt％CoSnO₃9.0-25.0 wt% of ZSM-5 molecular sieve containing mesopores-macropores; the active component contains 8.0-16.0 wt% of molybdenum, 1.5-5.0 wt% of cobalt and 0.2-3.5 wt% of magnesium.

4. The method of claim 1, wherein the hydrodesulfurization and isomerization catalyst comprises 75.0-87.0 wt.% Al based on the weight of the carrier₂O₃1.0-3.0 wt% of CoSnO₃1.0-4.5 wt% of La₂Sn₃O₇9.0-35.0 wt% of ZSM 5 molecular sieve containing mesopores-macropores; based on the catalyst, the active component contains 5.0-16.0 wt% of molybdenum, 1.5-6.0 wt% of cobalt, 2.5-8.5 wt% of nickel and 0.2-4.5 wt% of magnesium in terms of mass of oxides.

5. The process of hydro-upgrading of catalytically cracked gasoline of claim 4, wherein the support comprises 76.0-85.0 wt.% Al₂O₃，1.5-3.0wt％CoSnO₃，1.5-3.5wt％La₂Sn₃O₇9.0-25.0 wt% of ZSM 5 molecular sieve containing mesopores-macropores; the active component contains 8.0-16.0 wt% of molybdenum, 1.5-5.0 wt% of cobalt and 0.2-3.5 wt% of magnesium.

6. The process of hydro-upgrading of catalytically cracked gasoline of claim 2 or 4, wherein the CoSnO is CoSnO₃The preparation method comprises the following steps: respectively dissolving a tin source and a cobalt source, mixing and stirring uniformly, adding alkali liquor, reacting for 7-24h at the temperature of 120-180 ℃, cooling, washing and drying the obtained reactant to obtain precursor powder, and calcining the precursor powder at the temperature of 560-800 ℃ for 2-6h to obtain CoSnO₃。

7. The method for hydro-upgrading of catalytically cracked gasoline of claim 2 or 4, wherein the ZSM-5 molecular sieve containing meso-macropores has a pore size of2 to 70nm, and a total specific surface area of 300 to 350m²/g、360～400m²(ii)/g or 410 to 450m²/g。

8. The hydro-upgrading method for catalytically cracked gasoline according to claim 2 or 4, wherein the ZSM-5 molecular sieve containing meso-macropores has a pore volume of 0.20-0.24 m³/g、0.25～0.30m³A/g or 0.31 to 0.35m³/g。

9. The process for hydroupgrading of catalytically cracked gasoline according to claim 2 or 4, wherein in the hydrodesulfurization and isomerization catalyst, the amount of Co in the carrier is lower than the amount of Co supported by the catalyst, based on the mass of CoO.

10. The method for hydro-upgrading catalytically cracked gasoline as claimed in claim 2, wherein the method for preparing the gasoline hydrodesulfurization and isomerization catalyst comprises the following steps:

11. The method for hydro-upgrading catalytically cracked gasoline of claim 10, wherein in step (1), the pH of the acid solution containing styrene-butadiene rubber emulsion is below 6; in the step (3), the roasting conditions are as follows: 480-700 ℃ for 4-10 hours; in the step (4), the adding amount of a vulcanizing agent in the impregnation liquid is 80-130% of the theoretical sulfur-carrying amount of the catalyst; in the step (6), the vulcanization step is: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr to complete sulfurization; the temperature of the vacuum drying is 80-150 ℃.

12. The process for hydro-upgrading of catalytically cracked gasoline of claim 11, characterized in that the step of sulfiding is: refluxing the catalyst precursor at 65-75 deg.c for 0.5-1.5 hr, adding reductant to react at 100-140 deg.c for 2-6 hr and sulfurizing.

13. The method for hydro-upgrading catalytically cracked gasoline of claim 4, wherein the method for preparing the gasoline hydrodesulfurization and isomerization catalyst comprises the steps of:

(I) preparation of the carrier:

(II) preparation of catalyst:

14. The method for hydro-upgrading catalytically cracked gasoline of claim 13, wherein the amount of the sulfiding agent added in the impregnation liquid is 85-120% of the theoretical sulfur loading of the catalyst.

15. The method for hydro-upgrading catalytically cracked gasoline of claim 1, wherein the pre-hydrogenation catalyst is prepared by a process comprising the steps of:

16. The process for hydro-upgrading of catalytically cracked gasoline according to claim 1, characterized in that the pre-hydrotreating conditions are: the reaction temperature is 90-155 ℃, the reaction pressure is 1.5-4.5MPa, and the liquid volume space velocity is 2-7h^-1The volume ratio of hydrogen to oil is 4-7: 1;