A coupling catalyst for producing chemicals from FCC gasoline based on S-Zorb process, its preparation method and application

Abstract

The application discloses a kind of FCC gasoline production chemicals coupling catalyst based on S-Zorb process and its preparation method and application.Preparation by ion exchange method synthesis M2 / ZSM-5, then with nano zinc oxide through solid phase grinding way coupling calcination is obtained ZnO@M2 / ZSM-5, it is in the mixed solution containing M1 and Ni metal salt equal volume impregnation after calcination, again with diatomite dispersion grinding into M1Ni / ZnO@M2 / ZSM-5 catalyst.The catalyst prepared by the application utilizes the active component of reactive adsorption desulfurizer Ni / ZnO in S-Zorb process to realize in-situ removal of sulfur-containing components;Metal-modified high-acid ZSM-5 can improve the desulfurization performance of catalyst and strengthen the function of ZSM-5 aromatization, reforming, effectively inhibit the generation of coke, so that FCC gasoline is converted into aromatic hydrocarbons and other high value-added petrochemical products.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of petroleum chemical industry, in particular to a coupling catalyst for producing chemicals from FCC gasoline based on S-Zorb process and a preparation method and application thereof. BACKGROUND

[0002] In recent years, the demand for oil products has slowed down, and the demand for chemical products has increased. Under this background, refining and chemical integration has become an important development strategy for the petrochemical industry. Refining and chemical integration is an integrated mode that combines refining and chemical production, starting from crude oil and ending with chemical production. It reduces the yield of gasoline and diesel and increases the output of chemical products. Aromatic hydrocarbons are important chemical raw materials and are widely used, but the self-sufficiency rate in China is insufficient. Increasing the production of aromatic hydrocarbons is the main direction of controlling oil and increasing chemicals.

[0003] The main active component in S-Zorb process is Ni / ZnO, which realizes sulfur removal in FCC gasoline by reaction adsorption desulfurization, and the sulfur content is reduced to 1-10 ppm. Continuous reforming process device is the leading device for producing aromatic hydrocarbons, and the aromatic hydrocarbons produced account for about 30% of the global aromatic content. The reforming catalyst currently used is a dual-function catalyst, with noble metal Pt providing the metal active center and chlorine-containing alumina providing the acid active center. However, the high price of noble metals and the corrosion of free chlorine to equipment limit the development of reforming catalysts. The reforming raw material requires very low sulfur content. The process conditions of the two are similar, and the active component of the reaction adsorption desulfurizer Ni / ZnO in S-Zorb process removes sulfur, which can provide a low-sulfur or sulfur-free environment for reforming. If S-Zorb process is coupled with continuous reforming process, a coupling catalyst that produces aromatic hydrocarbons while upgrading gasoline can be prepared, and the purpose of producing high-value-added chemicals from FCC gasoline can be achieved through one-time feeding, exploring a new way for the utilization of FCC gasoline chemicals. SUMMARY

[0004] To solve the above technical problems, the present application provides a coupling catalyst for producing chemicals from FCC gasoline based on S-Zorb process and a preparation method and application thereof, and the technical scheme is as follows:

[0005] A preparation method of a coupling catalyst for producing chemicals from FCC gasoline based on S-Zorb process, comprising the following steps:

[0006] S1: exchanging the M2 metal cations in the solution with the cations of ZSM-5 by ion exchange method to obtain M2 / ZSM-5;

[0007] S2: coupling and calcining M2 / ZSM-5 and nano-zinc oxide by solid-phase grinding to obtain ZnO@M2 / ZSM-5 carrier;

[0008] S3: a mixed solution containing M1 metal salt and Ni metal salt is prepared, and the ZnO@M2 / ZSM-5 carrier is immersed in the mixed solution in an equal volume, and then calcined to obtain M1Ni / ZnO@M2 / ZSM-5;

[0009] S4: the M1Ni / ZnO@M2 / ZSM-5 is dispersed and ground with diatomite, and then calcined to obtain a M1Ni / ZnO@M2 / ZSM-5 coupling catalyst.

[0010] Further, the step S1 comprises the following operations: the M2 metal salt is dissolved in deionized water, and then stirred after oil bath heating after adding HZSM-5, and then the reaction product is obtained, and then washed with water, centrifuged, dried and calcined; the M2 metal salt contains one or more of various metal salts of Ni, Zn, Ga, Pt, Cu, Mo and Fe.

[0011] Further, the ZSM-5 molecular sieve is one or more of H-type ZSM-5 and Na-type ZSM-5, and the silicon-aluminum ratio is 20-300; the Ni-containing metal salt is one or more of nickel nitrate, nickel oxalate, nickel chloride and basic nickel carbonate; the Zn-containing metal salt is one or more of basic zinc carbonate, zinc nitrate and zinc oxalate; the Ga-containing metal salt is one or more of gallium chloride, gallium nitrate and gallium sulfate; and the Pt-containing metal salt is one or more of chloroplatinic acid, tetraammine platinum nitrate and platinum nitrate.

[0012] Further, the ion exchange temperature is 80-100℃, the drying temperature is 80-120℃, the drying time is 2-12h, the calcination temperature is 500-550℃, and the calcination time is 1-6h.

[0013] Further, in the step S2, the mass ratio of ZnO to M2 / ZSM-5 is 1 / 50-50 / 1, the calcination temperature is 500-550℃, the temperature rising rate is 1-5℃ / min, and the calcination time is 1-6h.

[0014] Further, in the step S3, the M1-containing metal salt is one or more of various metal salts of Pt, Zn, Ga, Fe, Cu and Mo; and the Ni-containing metal salt is one or more of nickel nitrate, nickel chloride, nickel acetate and basic nickel carbonate.

[0015] Further, in the step S3, the impregnation time is 10-15h, the drying temperature is 80-120℃, the drying time is 2-6h, the calcination temperature is 500-550℃, the temperature rising rate is 1-5℃ / min, and the calcination time is 1-6h.

[0016] Further, in the step S4, the calcination temperature is 500-550℃, the temperature rising rate is 1-5℃ / min, and the calcination time is 1-6h.

[0017] A coupling catalyst is prepared by the above-mentioned method for preparing a coupling catalyst for producing chemicals from FCC gasoline based on the S-Zorb process.

[0018] The above-mentioned coupling catalyst is used in the production of FCC gasoline, and when used as a main active component, it can be used alone or, according to the required catalyst properties of the reactor (fluidized bed, moving bed and fixed bed) for the reaction, it can be used after adding silica sol, alumina, aluminum sol or sesbania powder as an auxiliary catalyst after being shaped. -1 .

[0019] The present application mainly has the following beneficial technical effects:

[0020] 1. The coupling catalyst prepared by the present application uses the active component of the reaction adsorption desulfurizer Ni / ZnO in the S-Zorb process to realize in-situ removal of sulfur components, providing a low-sulfur environment for hydrocarbon reforming; the metal-modified high-acid ZSM-5 can improve the desulfurization performance of the catalyst and strengthen the aromatization and reforming functions of ZSM-5, effectively inhibiting the generation of coke, making the FCC gasoline converted into high-value-added petrochemical products such as aromatic hydrocarbons, and exploring a new way for the chemical utilization of FCC gasoline.

[0021] 2. The coupling catalyst prepared by the present application can deeply desulfurize gasoline, and the desulfurization rate is more than 95%.

[0022] 3. The coupling catalyst preparation method of the present application is reasonable, easy to operate, and conducive to popularization. DETAILED DESCRIPTION

[0023] In order for those skilled in the art to better understand the present application, the general embodiment of the present application will be introduced first, and then specific examples will be illustrated in the form of specific embodiments, which are only used for individual examples and do not constitute any form of limitation on the actual protection scope of the present application, nor limit the protection scope of the present application to this.

[0024] The overall embodiment of the present application is a preparation method of a coupling catalyst for producing chemicals from FCC gasoline based on the S-Zorb process, comprising the following steps: S1: exchanging M2 metal cations in a solution with cations of ZSM-5 by ion exchange to obtain M2 / ZSM-5; S2: coupling and calcining M2 / ZSM-5 with nano-zinc oxide by solid phase grinding to obtain a ZnO@M2 / ZSM-5 carrier; S3: preparing a mixed solution containing M1 metal salt and Ni metal salt, and then impregnating the ZnO@M2 / ZSM-5 carrier in the mixed solution in an equal volume and calcining to obtain M1Ni / ZnO@M2 / ZSM-5; and S4: coupling and calcining M1Ni / ZnO@M2 / ZSM-5 with diatomite by dispersion grinding to obtain a M1Ni / ZnO@M2 / ZSM-5 coupling catalyst. In step S1, the M2 metal salt is dissolved in deionized water, ZSM-5 is added, and then oil bath heating and stirring are performed, and the reaction product is washed with water, centrifuged, dried, and calcined; the M2 metal salt includes one or more of various metal salts of Ni, Zn, Ga, Pt, Cu, Mo, and Fe; the ZSM-5 molecular sieve is one or more of H-type ZSM-5 and Na-type ZSM-5, and the silicon-aluminum ratio is 20-300; the Ni-containing metal salt is one or more of nickel nitrate, nickel oxalate, nickel chloride, and basic nickel carbonate; the Zn-containing metal salt is one or more of zinc carbonate, zinc nitrate, and zinc oxalate; the Ga-containing metal salt is one or more of gallium chloride, gallium nitrate, and gallium sulfate; the Pt-containing metal salt is one or more of chloroplatinic acid, tetraammine platinum nitrate, and platinum nitrate; the ion exchange temperature is 80-100 DEG C; the drying temperature is 80-120 DEG C, and the drying time is 2-12 h; and the calcination temperature is 500-550 DEG C, and the calcination time is 1-6 h. In step S2, the mass ratio of ZnO to M2 / ZSM-5 is 1 / 50-50 / 1; the calcination temperature is 500-550 DEG C, the temperature rising rate is 1-5 DEG C / min, and the calcination time is 1-6 h. In step S3, the M1-containing metal salt is one or more of various metal salts of Pt, Zn, Ga, Fe, Cu, and Mo; the Ni-containing metal salt is one or more of nickel nitrate, nickel chloride, nickel acetate, and basic nickel carbonate; the impregnation time is 10-15 h; the drying temperature is 80-120 DEG C, and the drying time is 2-6 h; the calcination temperature is 500-550 DEG C, the temperature rising rate is 1-5 DEG C / min, and the calcination time is 1-6 h. In step S4, the calcination temperature is 500-550 DEG C, the temperature rising rate is 1-5 DEG C / min, and the calcination time is 1-6 h.The application of the coupling catalyst prepared by the method in the production of FCC gasoline: the coupling catalyst can be used alone as the main active component; or the coupling catalyst can be used after being added with silica sol, alumina, aluminum sol or sesbania powder as an auxiliary catalyst according to the required catalyst properties of the reactor (fluidized bed, moving bed and fixed bed) for the reaction, so as to be shaped; the aromatization reaction temperature of the catalytic cracking gasoline is 470-570 ℃, the hydrogen partial pressure is 0.5-2 MPa, the hydrogen / oil ratio is 100 / 1-1000 / 1, and the mass space velocity is 1-8 h. -1 .

[0025] In addition, for the coupling catalyst M1Ni / ZnO @M2 / ZSM-5, the second metal M1 can also be selected not to be added during the preparation. Example 1

[0026] The embodiment provides a preparation method of a PtNi / ZnO@Zn / ZSM-5 coupling catalyst for producing FCC gasoline chemicals based on an S-Zorb process, which comprises the following steps:

[0027] First, 3.64 g of zinc nitrate and 400 ml of deionized water are weighed and stirred uniformly, 40 g of ZSM-5 is added and stirred in an 80 ℃ oil bath for 8 h, washed with water and centrifuged three times, dried at 80 ℃ for 12 h, and then placed in a muffle furnace and calcined at 550 ℃ with a temperature rising rate of 2 ℃ / min for 4 h to obtain Zn / ZSM-5.

[0028] After 20 g of Zn / ZSM-5 and 10 g of nano-zinc oxide are ground in a solid-phase grinder for 3 h, the mixture is placed in a muffle furnace and calcined at 550 ℃ with a temperature rising rate of 2 ℃ / min for 4 h to obtain a ZnO@Zn / ZSM-5 carrier.

[0029] 1 g of chloroplatinic acid is dissolved in a 25 ml volumetric flask to prepare a chloroplatinic acid solution, 3.96 g of nickel nitrate and 12.3 ml of deionized water are weighed and stirred uniformly in a beaker, 5.31 ml of the chloroplatinic acid solution is measured and placed in the beaker, and then the above-mentioned mixed solution is uniformly added to the ZnO@Zn / ZSM-5 carrier, and after being naturally air-dried for 12 h, the mixture is placed in a drying box and dried for 4 h, and then placed in a muffle furnace and calcined at 550 ℃ with a temperature rising rate of 2 ℃ / min for 4 h to obtain PtNi / ZnO@Zn / ZSM-5.

[0030] After 1.6 g of PtNi / ZnO@Zn / ZSM-5 and 0.4 g of diatomite are dispersed and ground, a NiPt / ZnO@Zn / ZSM-5 coupling catalyst is obtained. Example 2

[0031] The embodiment provides a preparation method of a NiPt / ZnO@Ga / ZSM-5 catalyst for producing chemicals from catalytic cracking gasoline based on an S-Zorb process device, and the method comprises the following steps:

[0032] First, 2.94g of gallium nitrate and 400ml of deionized water are stirred uniformly, 40g of ZSM-5 is added in an 80 DEG C oil bath pot and stirred for 8h, centrifugal washing is performed three times, drying is performed at 80 DEG C for 12h, and then the ZSM-5 is placed in a muffle furnace and calcined at 550 DEG C with a temperature increasing rate of 2 DEG C / min for 4h to obtain Ga / ZSM-5.

[0033] 20g of Ga / ZSM-5 and 10g of nano zinc oxide are placed in a solid-phase grinder and ground for 3h, and then the mixture is placed in a muffle furnace and calcined at 550 DEG C with a temperature increasing rate of 2 DEG C / min for 4h to obtain a ZnO@Ga / ZSM-5 carrier.

[0034] 1g of chloroplatinic acid is dissolved in a 25ml volumetric flask to prepare a chloroplatinic acid solution, 3.96g of nickel nitrate and 12.3ml of deionized water are stirred uniformly in a beaker, 5.31ml of the chloroplatinic acid solution is measured and added to the beaker, the mixture is uniformly added dropwise to the ZnO@Ga / ZSM-5 carrier, the mixture is naturally air-dried for 12h, then the mixture is placed in a drying box and dried for 4h, and then the mixture is placed in a muffle furnace and calcined at 550 DEG C with a temperature increasing rate of 2 DEG C / min for 4h to obtain PtNi / ZnO@Ga / ZSM-5.

[0035] 1.6g of PtNi / ZnO@Ga / ZSM-5 and 0.4g of diatomite are dispersed and ground to obtain a NiPt / ZnO@Ga / ZSM-5 coupling catalyst. Example 3

[0036] The embodiment provides a preparation method of a Ni / ZnO@Ni / ZSM-5 catalyst for producing chemicals from catalytic cracking gasoline based on an S-Zorb process device, and the method comprises the following steps:

[0037] First, 3.92g of nickel nitrate and 400ml of deionized water are stirred uniformly, 40g of ZSM-5 is added in an 80 DEG C oil bath pot and stirred for 8h, centrifugal washing is performed three times, drying is performed at 80 DEG C for 12h, and then the ZSM-5 is placed in a muffle furnace and calcined at 550 DEG C with a temperature increasing rate of 2 DEG C / min for 4h to obtain Ni / ZSM-5.

[0038] 20g of Ni / ZSM-5 and 10g of nano zinc oxide are placed in a solid-phase grinder and ground for 3h, and then the mixture is placed in a muffle furnace and calcined at 550 DEG C with a temperature increasing rate of 2 DEG C / min for 4h to obtain a ZnO@Ni / ZSM-5 carrier.

[0039] Take 3.96 g of nickel nitrate and 17.6 ml of deionized water to prepare an impregnation solution, which is uniformly added to the ZnO@Ni / ZSM-5 carrier, and then placed at room temperature for 12 h, dried at 80℃ for 3 h, and then placed in a muffle furnace and calcined at 550℃ for 4 h at a heating rate of 2℃ / min to obtain Ni / ZnO@Ni / ZSM-5.

[0040] After dispersing and grinding 1.6 g of Ni / ZnO@Ni / ZSM-5 and 0.4 g of diatomite, a Ni / ZnO@Ni / ZSM-5 coupling catalyst is obtained. Example 4

[0041] This example proposes a preparation method of a Ni / ZnO@Zn / ZSM-5 catalyst for producing chemicals from catalytic cracking gasoline based on an S-Zorb process device, which comprises the following steps:

[0042] First, 3.64 g of zinc nitrate and 400 ml of deionized water are stirred uniformly, 40 g of ZSM-5 is added and stirred in an 80℃ oil bath for 8 h, washed with water and centrifuged three times, dried at 80℃ for 12 h, and then placed in a muffle furnace and calcined at 550℃ for 4 h at a heating rate of 2℃ / min to obtain Zn / ZSM-5.

[0043] After taking 20 g of Zn / ZSM-5 and 10 g of nano-zinc oxide and placing them in a solid-phase grinder for grinding for 3 h, they are placed in a muffle furnace and calcined at 550℃ for 4 h at a heating rate of 2℃ / min to obtain a ZnO@Zn / ZSM-5 carrier.

[0044] Take 3.96 g of nickel nitrate and 17.6 ml of deionized water to prepare an impregnation solution, which is uniformly added to the ZnO@Zn / ZSM-5 carrier, and then placed at room temperature for 12 h, dried at 80℃ for 3 h, and then placed in a muffle furnace and calcined at 550℃ for 4 h at a heating rate of 2℃ / min to obtain Ni / ZnO@Zn / ZSM-5.

[0045] After dispersing and grinding 1.6 g of Ni / ZnO@Zn / ZSM-5 and 0.4 g of diatomite, a Ni / ZnO@Ni / ZSM-5 coupling catalyst is obtained.

[0046] The catalysts in the above examples 1, 2, 3, and 4 are pressed into tablets, and then sieved into particles with a size of 20-40 mesh. The FCC gasoline from the Rizhao Refinery (sulfur content 1186 ppm, alkane content 39.41%, naphthene content 7.12%, olefin content 24.25%, and aromatic content 29.22%) is used as the raw material, and a fixed bed reactor is used for evaluation. The operation conditions are as follows: reaction temperature 530℃, hydrogen partial pressure 1 MPa, hydrogen / oil ratio 100 / 1, and mass space velocity 4 h-1. -1 The evaluation results are shown in Tables 1 and 2.

[0047] Table 1 FCC gasoline cracking product distribution

[0048]

[0049] Table 2 C5 of different metal modified HZSM-5 + Crude gasoline product distribution table

[0050]

[0051] From the results of Table 1 and Table 2, it can be seen that the metal modified ZSM-5 molecular sieve based coupling S-Zorb catalyst provided by the present application can realize deep desulfurization (desulfurization rate of more than 95%) while producing aromatics, and the produced ethane and propane can be further used as important raw materials for producing ethylene and propylene.

[0052] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements are also considered within the protection scope of the present application.

Claims

1. Use of a coupled catalyst in the production of FCC gasoline based chemicals based on the S-Zorb process, characterized in that, The preparation method of the coupling catalyst comprises the following steps: S1: ion exchange reaction of M2 metal cations in solution with cations of ZSM-5 by ion exchange method to obtain M2 / ZSM-5; including the following operations: dissolving M2 metal salt in deionized water, adding ZSM-5, heating and stirring in oil bath, and then washing with water, centrifuging, drying and calcining after obtaining the reaction product; the M2 metal salt includes one or more of various metal salts of Ni, Zn and Ga; S2: coupling calcination of M2 / ZSM-5 and nano-zinc oxide by solid phase grinding to obtain ZnO@M2 / ZSM-5 carrier; S3: preparing a mixed solution containing M1 metal salt and Ni-containing metal salt, and then impregnating the ZnO@M2 / ZSM-5 carrier in the mixed solution with equal volume and calcining to obtain M1Ni / ZnO@M2 / ZSM-5; the M1 metal salt is one or more of various metal salts of Pt, and the Ni-containing metal salt is one or more of nickel nitrate, nickel chloride, nickel acetate and basic nickel carbonate; S4: dispersing and grinding M1Ni / ZnO@M2 / ZSM-5 with diatomite and calcining to obtain M1Ni / ZnO@M2 / ZSM-5 coupling catalyst.

2. Use of a coupled catalyst according to claim 1 in the production of FCC gasoline based chemicals based on the S-Zorb process, characterized in that, The ion exchange reaction temperature in step S1 is 80-100℃, the drying temperature is 80-120℃, the drying time is 2-12h, the calcination temperature is 500-550℃, and the calcination time is 1-6h.

3. Use of a coupled catalyst according to claim 1 in the production of chemicals based on the S-Zorb process of FCC gasoline, characterized in that, The mass ratio of ZnO to M2 / ZSM-5 in step S2 is 1 / 50-50 / 1, the calcination temperature is 500-550℃, the heating rate is 1-5℃ / min, and the calcination time is 1-6h.

4. Use of a coupled catalyst according to claim 1 in the production of chemicals based on the S-Zorb process of FCC gasoline, characterized in that, The impregnation time in step S3 is 10-15h, the calcination temperature is 500-550℃, the heating rate is 1-5℃ / min, and the calcination time is 1-6h.

5. Use of a coupled catalyst according to claim 1 in the production of chemicals based on FCC gasoline according to the S-Zorb process, characterized in that, The calcination temperature in step S4 is 500-550℃, the heating rate is 1-5℃ / min, and the calcination time is 1-6h.

6. Use of a coupled catalyst according to claim 1 in the production of chemicals based on the S-Zorb process of FCC gasoline, characterized in that, The coupling catalyst uses silica sol, alumina, aluminum sol or sesbania powder as an auxiliary catalyst after shaping according to the catalyst properties required by the reactor for the reaction, as the main active component; the catalytic cracking gasoline aromatization reaction temperature is 470-570°C, the hydrogen partial pressure is 0.5-2 MPa, the hydrogen / oil ratio is 100 / 1-1000 / 1, and the mass space velocity is 1-8 h -1 .

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