CN109304207B - Catalytic cracking catalyst for cracking coker gas oil and preparation method thereof - Google Patents

Catalytic cracking catalyst for cracking coker gas oil and preparation method thereof Download PDF

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CN109304207B
CN109304207B CN201710630463.XA CN201710630463A CN109304207B CN 109304207 B CN109304207 B CN 109304207B CN 201710630463 A CN201710630463 A CN 201710630463A CN 109304207 B CN109304207 B CN 109304207B
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molecular sieve
rare earth
phosphorus
magnesium
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CN109304207A (en
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谭争国
潘志爽
袁程远
张海涛
高雄厚
张忠东
李雪礼
段宏昌
黄校亮
高永福
郑云锋
孙书红
张君屹
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a catalytic cracking catalyst for cracking coker gas oil and a preparation method thereof. The catalyst contains 15-70 wt% of molecular sieve, 15-60 wt% of clay, 8-30 wt% of pseudoboehmite and 3-20 wt% of binder, and the preparation method comprises the following steps: preparing a rare earth, phosphorus and magnesium composite modified Y-shaped molecular sieve, which is characterized in that the phosphorus modification of the molecular sieve is performed before the magnesium modification; then mixing and pulping the modified Y-type molecular sieve containing rare earth, phosphorus and magnesium, clay, pseudo-boehmite and a binder, and then sequentially carrying out spray drying, washing, filtering and drying to obtain the catalyst. The catalyst provided by the invention can reduce the adsorption capacity of nitride and aromatic hydrocarbon in the coker gas oil and the acid center of the catalyst, reduce the negative influence of the coker gas oil on the catalytic cracking reaction, and has excellent coke selectivity under the conditions of improving the conversion rate and reducing the heavy oil.

Description

Catalytic cracking catalyst for cracking coker gas oil and preparation method thereof
Technical Field
The invention relates to a catalytic cracking catalyst and a preparation method thereof, in particular to a cracking coking wax oil catalyst and a preparation method thereof.
Background
Delayed coking is currently an important resid upgrading process. With crude oil quality degradation and price reduction, delayed coking has become more popular in current refining programs due to the flexibility of processing feedstocks. The delayed coking processing capacity has increased dramatically in china, reaching 11000 million tons in 2010. Coker Gas Oil (CGO) is the major product of delayed coking processes, accounting for 20-30 wt% of the coker product, and the utilization of coker gas oil directly affects the economic benefits of refineries.
In foreign countries, coker gas oil is used as a catalytic cracking feedstock via hydrotreating. For example, in the united states, more than 50% of the catalytic cracking feedstock is hydrotreated, while in europe 10% of the catalytic feedstock is hydrotreated. In China, due to the shortage of a hydrocracking device and high operation cost, the catalytic cracking device is more practical to blend coking wax oil. However, compared with straight run wax oil, the coker wax oil has a higher aromatic content, nitrogen content, especially basic nitrogen content, typically about 30%, and nitrogen content of about 0.35%. The alkali nitrogen compound is adsorbed on the acid center of the catalyst to reduce the number of active centers and reduce the catalytic cracking conversion rate and the product yield; and non-alkali nitrogen compounds and aromatic hydrocarbons deposit on the surface of the catalyst to form coke, so that other hydrocarbon substances are prevented from contacting with acid centers, and the conversion rate of catalytic cracking is influenced. In view of the characteristics of coker gas oil, some process improvement methods have been proposed, such as catalytic cracking adsorption conversion (DNCC) process [ Zhang, r.c.; shi, w.y.refined Catalytic Cracking (DNCC) Technology for Coker Gas Oil processing.pet.process.petrochem.1998,29,22-27 ], two-stage riser Catalytic Cracking process (TSR) [ Yuan, q.m.; wang, y.l.; li, c.y.; yang, c.h.; shan, h.h.study on conversion of linker gas oil by two-stage catalytic cracking.j.china univ.pet. (ed.nat. sci.), 2007,31(1), 122-; wang, g.; liu, y.d.; wang, h.; liang, y.m.; xu, c.m.; gao, j.s.catalytic cracking catalysts and division of catalytic cracking process for coker gas oil. energy Fuels2012, (26) (4), 2281-; shan, h.h.; liu, w.j.; chen, x.b.; li, c.y.; yang, C.H.Synthesis Process for Coker Gas Oil Catalytic Cracking and Gasoline reforming. energy Fuels2013,27(2), 654-. The process needs to modify the existing device in practical application, increases the investment of a refinery and has large risk. Therefore, the development of a high-efficiency cracking coker gas oil catalyst is undoubtedly a simple approach to solving the problem of coker gas oil.
CN 103084205A discloses a cracking catalyst of alkali-nitrogen resistant prolific liquefied gas and a preparation method thereof, the catalyst comprises a cracking active component, a mesoporous silicon-aluminum material, a binder and clay, wherein the cracking active component comprises a Y-type molecular sieve and an MFI structure molecular sieve, the Y-type molecular sieve comprises 8-23 wt% of rare earth content calculated by rare earth oxide, and Fe content calculated by Fe2O30.1-3.0 wt% calculated as CuO, 0-3.0 wt% calculated as Cu, and P2O5Calculated as 0-2.0 wt% and 0.1-2.5 wt% sodium oxide. The preparation method of the catalyst comprises the steps of pulping the cracking active component, the mesoporous silicon-aluminum material, the clay and the binder, spray drying, washing, filtering and drying. The catalyst is used for the catalytic cracking of the basic nitrogen-containing raw oil, and has higher conversion rate and higher liquefied gas yield.
CN 103084206A discloses a catalytic cracking catalyst for resisting alkali-nitrogen and producing diesel oil in high yield and a preparation method thereof, wherein the catalyst comprises a cracking active component, a mesoporous silicon-aluminum material, a binder and clay, wherein the cracking activity is as followsThe component comprises a first Y-type molecular sieve and a second Y-type molecular sieve, and optionally a third Y-type molecular sieve, wherein the rare earth content in the first molecular sieve is 8-23 wt% calculated by rare earth oxide, and the iron content is Fe2O3Calculated as CuO, 0.1-3.0 wt%, copper content calculated as CuO, and phosphorus content calculated as P2O5Calculated as 0-2.0 wt%, the sodium oxide content is 0.1-2.5 wt%; the second Y-type molecular sieve is an ultrastable Y-type molecular sieve containing magnesium, and the third Y-type molecular sieve is a DASY molecular sieve containing rare earth. The preparation method of the catalyst comprises the steps of pulping the cracking active component, the mesoporous silicon-aluminum material, the clay and the binder, spray drying, washing, filtering and drying. The catalyst is used for catalytic cracking of hydrocarbon oil with high alkali nitrogen content, and has high conversion rate and diesel oil yield.
CN103084207A discloses a catalytic cracking catalyst for alkali nitrogen resistant gasoline with high yield and a preparation method thereof, wherein the catalyst comprises a cracking active component, a mesoporous silicon-aluminum material, a binder and clay, wherein the cracking active component comprises a first Y-type molecular sieve and an ultrastable Y-type molecular sieve containing rare earth, the rare earth content in the first Y-type molecular sieve is 8-23 wt% calculated by the weight of rare earth oxide, and the iron content is Fe2O3Calculated as CuO, 0.1-3.0 wt%, copper content calculated as CuO, and phosphorus content calculated as P2O5Calculated as 0-2.0 wt%, and the content of sodium oxide is 0.1-2.5 wt%. The preparation method of the catalyst comprises the steps of pulping the cracking active component, the mesoporous silicon-aluminum material, the clay and the binder, spray drying, washing, filtering and drying. The catalyst is used for catalytic cracking of hydrocarbon oil with high alkali nitrogen content, and has higher conversion rate and gasoline yield.
CN103084200A discloses an alkali-nitrogen resistant catalytic cracking catalyst and a preparation method thereof, wherein the catalyst comprises cracking active components, clay and a binder, and contains or does not contain a mesoporous silicon-aluminum material; wherein the cracking active component comprises a Y-shaped molecular sieve modified by rare earth, iron, copper and phosphorus, the content of the rare earth in the molecular sieve is 8-23 wt% calculated by rare earth oxide, and the content of the iron is Fe2O3Calculated as 0.1-3.0 wt%, copper content0 to 3.0 wt.% calculated as CuO, the phosphorus content being expressed as P2O5Calculated as 0-2.0 wt%, and the content of sodium oxide is 0.1-2.5 wt%. The preparation method comprises the steps of mixing and pulping the cracking active component, the mesoporous silicon-aluminum material, the clay and the binder, and then sequentially carrying out spray drying, washing, filtering and drying.
The above patents all adopt rare earth modification to improve the activity stability of the molecular sieve, and introduce iron/copper/phosphorus to adjust the strength and density of the acid center; iron and/or copper ions with a d-empty orbit in the nuclear electron distribution form a complex with a nitrogen atom containing lone pair electrons to selectively adsorb the alkaline nitride, so that the toxic action of the alkaline nitrogen on the acid center of the catalyst is reduced. The catalyst prepared by the method of the above patent inevitably prevents other hydrocarbon molecules from contacting with the acidic center of the catalyst when the catalyst acts with the alkali nitrogen compound due to the large molecular size of the alkali compound, and the influence of the aromatic hydrocarbon and the non-alkali nitrogen compound in the coker gas oil on the catalytic cracking is not considered in the above patent.
Disclosure of Invention
The invention aims to provide a catalytic cracking catalyst for cracking coker gas oil and a preparation method thereof, wherein the catalyst can reduce the adsorption capacity of nitride and aromatic hydrocarbon in the coker gas oil and an acid center of the catalyst, reduce the negative influence of the coker gas oil on a catalytic cracking reaction, and improve the heavy oil conversion capacity.
The invention provides a preparation method of a catalytic cracking catalyst for cracking coker gas oil, which comprises the following steps: (1) preparing a rare earth, phosphorus and magnesium composite modified Y-type molecular sieve: (a) carrying out ion exchange on the NaY molecular sieve and an ammonium salt solution, filtering, washing, mixing a washed filter cake with rare earth salt, and then roasting for 1-3 hours at the temperature of 400 ℃ and 700 ℃ under 1-50% of water vapor to obtain the rare earth modified Y-type molecular sieve; (b) performing ion exchange on the rare earth modified Y-type molecular sieve obtained in the step (a) and a phosphorus-containing compound or a mixed solution of the phosphorus-containing compound and an ammonium salt, filtering, washing, and roasting for 0.5-3 hours at the temperature of 600 ℃ and under the condition of l-100% of water vapor to obtain the rare earth and phosphorus composite modified Y-type molecular sieve; (c) and (c) carrying out ion exchange on the Y-shaped molecular sieve compositely modified by the rare earth and the phosphorus obtained in the step (b) and a magnesium salt solution, and then filtering and washing to obtain the Y-shaped molecular sieve compositely modified by the rare earth, the phosphorus and the magnesium. (2) Preparing a catalyst: mixing and pulping the molecular sieve, the clay, the pseudo-boehmite and the binder, and then sequentially carrying out spray drying, washing, filtering and drying to prepare the catalytic cracking catalyst for cracking the coker gas oil.
In the method provided by the invention, the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1) is prepared by exchanging ions according to ammonium salt: NaY molecular sieve: deionized water 0.15-1: l:1-50, preferably 0.2-0.5:1:2-30, mixing ammonium salt, NaY molecular sieve and deionized water, pulping, adjusting pH value of the pulp to 2.0-6.0, preferably 3.0-5.0, exchanging at 40-130 deg.C, preferably 60-90 deg.C for 0.5-4 hours, preferably 1-3 hours.
In the method provided by the invention, the washed filter cake prepared by the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1) is mixed with rare earth salt according to the rare earth salt (RE is used as the RE)2O3Meter): NaY molecular sieve 0.001-0.2: l, preferably 0.02-0.2: 1.
In the method provided by the invention, in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1), the ion exchange in the step (b) is carried out according to a phosphorus-containing compound (calculated as P): ammonium salt: NaY molecular sieve: deionized water 0.001-0.1:0-0.3:1:1-50, preferably 0.005-0.04:0-0.2:1:2-30, mixing and pulping the phosphorus-containing compound, the ammonium salt, the NaY molecular sieve and the deionized water uniformly, adjusting the pH value of the pulp to 2.0-6.0, preferably 3.0-5.0, and exchanging for 0.5-3 hours, preferably 1-2 hours at 40-130 ℃, preferably 60-90 ℃.
In the method provided by the invention, in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1), the ion exchange in the step (c) is carried out according to the following magnesium salt (calculated by Mg): NaY molecular sieve: deionized water 0.001-0.05:1:1-50, preferably 0.003-0.03:1:2-20, mixing magnesium salt, NaY molecular sieve and deionized water, pulping, adjusting pH value of the slurry to 2.0-6.0, preferably 3.0-5.0, exchanging at 60-150 deg.C, preferably 70-100 deg.C for 0.5-3 hours, preferably 1-2 hours.
In the method provided by the invention, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium oxalate and ammonium phosphate.
In the method provided by the invention, the rare earth salt is one or more of chloride, nitrate and sulfate of rare earth, and preferably chloride. Wherein the rare earth is preferably lanthanum and/or cerium.
In the method provided by the invention, the phosphorus compound is selected from one or more of orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and pyrophosphoric acid.
In the method provided by the invention, the magnesium salt is selected from one or more of magnesium chloride, magnesium nitrate, magnesium hydroxychloride and magnesium sulfate, and preferably magnesium chloride.
In the method provided by the invention, the molecular sieve contains a rare earth, phosphorus and magnesium modified Y-type molecular sieve and a conventional molecular sieve. In the rare earth, phosphorus and magnesium modified Y-type molecular sieve, the content of rare earth is 2-20 wt% calculated by rare earth oxide, the content of phosphorus is 0.1-10 wt% calculated by phosphorus, the content of magnesium is 0.1-5 wt% calculated by magnesium, and the content of sodium oxide is 0.05-1.0 wt% calculated by sodium. The conventional molecular sieve is one or a mixture of more of conventional modified Y-type zeolite, ZSM zeolite, beta zeolite, omega zeolite, MCM zeolite and SAPO zeolite. Wherein the conventional modified Y-type zeolite is HY and NH4One of Y, REY, USY, REUSY, or their mixture. The molecular sieve comprises 20-100 wt% of the Y-type molecular sieve modified by rare earth, phosphorus and magnesium and 0-80 wt% of conventional molecular sieve based on dry weight.
In the method provided by the invention, the clay is kaolin, sepiolite, halloysite, montmorillonite or acid-modified clay thereof; preferably acid-modified kaolin, acid-modified halloysite, or mixtures thereof. The acid modified clay process comprises the following steps: calcining the clay for 1-5h at the temperature of 600-1000 ℃, and then mixing the clay: water: the mass ratio of concentrated hydrochloric acid or concentrated nitric acid is 1:3-10:0.05-2, and the acid modified clay is prepared after the reaction for 1-6 hours at the constant temperature of 60-90 ℃.
In the method provided by the invention, the pseudoboehmite can be one or the combination of boehmite, gibbsite and bayer stone, and is preferably boehmite.
In the method provided by the invention, the binder is one or a mixture of aluminum sol, basic aluminum chloride and silica sol.
In the method provided by the invention, the preparation methods of the catalyst can be implemented by adopting conventional methods, and specific implementation methods of the methods are described in detail in CN98117896.0, CN02103907.0 and CN200610112685.4, which are all incorporated by reference in the invention.
The catalytic cracking catalyst for the cracked coker gas oil provided by the invention contains a molecular sieve, clay, pseudo-boehmite and a binder, and comprises the following components, by mass, of 15-70% of the molecular sieve, 15-60% of the clay, 8-30% of the pseudo-boehmite and 3-20% of the binder on a dry basis. The catalyst can also contain 0-8 wt% of rare earth metal oxide, wherein the rare earth element in the rare earth metal oxide is selected from one or the combination of La, Ce, Pr and Nd.
The molecular sieve contained in the catalyst provided by the invention comprises a Y-shaped molecular sieve modified by rare earth, phosphorus and magnesium, wherein the molecular sieve firstly introduces rare earth elements to improve the activity stability of the molecular sieve, then introduces phosphorus to adjust the acid strength of the surface of the molecular sieve, and finally introduces magnesium to adjust the acid strength in a micropore channel of the molecular sieve, so that the adsorption capacity of an alkali nitrogen compound, polycyclic aromatic hydrocarbon and an acid center of the catalyst in coking wax oil is reduced, the retention time of the alkali nitrogen compound and the polycyclic aromatic hydrocarbon on the surface of the catalyst is reduced, the coking condensation reaction of the alkali nitrogen compound and the polycyclic aromatic hydrocarbon on the surface of the catalyst is inhibited, the coke blocking phenomenon is reduced, the utilization rate of a cracking center of the catalyst is improved, and the heavy oil conversion.
Detailed Description
The following examples further illustrate the features of the present invention, but the scope of the present invention is not limited by these examples.
Evaluation methods used in (A) examples
Catalytic crackingEvaluation of selectivity of chemical reaction: the catalyst cracking reaction selectivity evaluation was performed in a small Fixed Fluidized Bed (FFB) unit. The catalyst is treated for 10 hours at 800 ℃ under the condition of 100 percent of water vapor in advance. The reaction raw material oil is a Uruguaqin petrochemical catalytic raw material, the specific composition comprises 40% of vacuum residue oil, 30% of straight-run wax oil and 30% of coking wax oil, the properties are shown in Table 1, the reaction temperature is 500-535 ℃, and the airspeed is 12-15 h-1The solvent-oil ratio is 5.
TABLE 1 Properties of the stock oils
Figure BDA0001363731740000071
Production area and specification of raw materials used in example
Kaolin: china kaolin company, kaolinite 86 wt%.
And (3) trachelospermi: china kaolin, elsholtzia 80 wt%.
USY zeolite, REY zeolite and ZSM-5 are all produced by catalyst factories of Lanzhou petrochemical company.
Aluminum sol, hydrochloric acid, sulfuric acid, chlorinated rare earth, phosphoric acid, water glass and alkaline silica sol: industrial products from catalyst factories of landlocked petrochemical company.
Pseudo-boehmite: 75.4 wt% of alumina, produced by Shandong alumina works.
NaY molecular sieve, alumina sol: industrial products from catalyst factories of landlocked petrochemical company.
Ammonium sulfate, diammonium hydrogen phosphate, magnesium chloride, ammonium chloride, cerium nitrate, lanthanum nitrate, ammonium phosphate, lanthanum chloride, magnesium nitrate, ammonium carbonate, phosphoric acid, magnesium sulfate, ammonium nitrate, ammonium bisulfate, ferric nitrate, copper chloride: pure analysis, and is produced in Beijing chemical plants.
Example 1
Preparing a rare earth, phosphorus and magnesium modified Y-type molecular sieve:
taking 1000 g of NaY molecular sieve (dry basis), pulping with 10 kg of deionized water, adding 300 g of ammonium sulfate, adjusting the pH value to 3.5, exchanging for 1 hour at 90 ℃, filtering and washing with water, then mixing a filter cake with 100 g of lanthanum chloride (calculated by rare earth oxide), and roasting for 2 hours at 650 ℃ and 30% of water vapor to obtain the rare earth modified molecular sieve; pulping the roasted sample obtained by the previous step with 5 kg of deionized water, adding 50 g of diammonium hydrogen phosphate (calculated by phosphorus), adjusting the pH value to 4.0, exchanging for 1 hour at 80 ℃, filtering and washing with water, and roasting the filter cake for 1 hour at 600 ℃ to obtain the phosphorus-rare earth modified molecular sieve; mixing and pulping the phosphorus-rare earth modified molecular sieve with 8 kg of deionized water and 20 g of magnesium chloride (calculated by magnesium), adjusting the pH value to 3.8, reacting for 1 hour at 95 ℃, filtering and washing to obtain the rare earth-phosphorus-magnesium composite modified molecular sieve Y1.
Preparation of acid-modified clay:
500 g of kaolin which is roasted for 5 hours at the temperature of 600 ℃ is taken, 5000 kg of deionized water is used for pulping, 1000 g of concentrated hydrochloric acid is added, and the reaction is carried out for 6 hours at the temperature of 60 ℃ to obtain the acid modified clay N1.
Preparing a catalyst:
adding 2000 g of deionized water, 80 g of rare earth solution dry basis, 200 g of aluminum sol dry basis, 400 g of pseudo-boehmite dry basis, 600 g of the acid modified clay N1 dry basis, 650 g of the rare earth, phosphorus and magnesium modified molecular sieve Y1 dry basis and 70 g of USY dry basis into a reaction kettle, pulping for 60 minutes, uniformly stirring, and performing spray drying to obtain the FCC catalyst which is marked as C1 and prepared by the method.
Example 2
Preparing a rare earth, phosphorus and magnesium modified Y-type molecular sieve:
taking 1000 g of NaY molecular sieve (dry basis), pulping with 50 kg of deionized water, adding 150 g of ammonium chloride, adjusting the pH value to 2.1, exchanging for 4 hours at 45 ℃, filtering and washing with water, then mixing a filter cake with 100 g of lanthanum nitrate and 200 g of cerium nitrate (calculated by rare earth oxide), and roasting for 3 hours at 400 ℃ to obtain the rare earth modified molecular sieve; pulping the roasted sample with 50 kg of deionized water, adding 100 g of ammonium phosphate (calculated by phosphorus), adjusting the pH value to 2.0, exchanging at 130 ℃ for 0.5 hour, filtering and washing with water, and roasting a filter cake at 600 ℃ and 100% of water vapor for 0.5 hour to obtain the phosphorus-rare earth modified molecular sieve; mixing and pulping the phosphorus rare earth modified molecular sieve with 50 kg of deionized water and 50 g of magnesium nitrate (calculated as magnesium), adjusting the pH value to 2.0, reacting for 0.5 hour at 150 ℃, filtering and washing to obtain the rare earth, phosphorus and magnesium composite modified molecular sieve Y2.
Preparation of acid-modified clay:
500 g of halloysite calcined at 1000 ℃ for 1 hour is taken, 1500 g of deionized water is used for pulping, 50 g of concentrated nitric acid is added, and the reaction is carried out at 90 ℃ for 1 hour to obtain the acid modified clay N2.
Preparing a catalyst:
2000 g of deionized water, 160 g of rare earth solution dry basis, 60 g of aluminum sol dry basis, 600 g of pseudo-boehmite dry basis, 150 g of the acid modified clay N2 dry basis and 1030 g of the rare earth, phosphorus and magnesium modified molecular sieve Y2 dry basis are added into a reaction kettle, and the FCC catalyst prepared by the method is obtained after 60 minutes of pulping and uniform stirring and spray drying, and is marked as C2.
Example 3
Preparing a rare earth, phosphorus and magnesium modified Y-type molecular sieve:
taking 1000 g of NaY molecular sieve (dry basis), pulping with 1 kg of deionized water, adding 1000 g of ammonium carbonate, adjusting the pH value to 5.8, exchanging for 0.5 hour at 130 ℃, filtering and washing with water, then mixing a filter cake with 10 g of cerium nitrate (calculated by rare earth oxide), and roasting for 1 hour at 700 ℃ and 50% of water vapor to obtain the rare earth modified molecular sieve; pulping the roasted sample obtained by the previous step with 2 kg of deionized water, adding 10 g of phosphoric acid (calculated by phosphorus), adjusting the pH value to 5.9, exchanging for 3 hours at 40 ℃, filtering and washing with water, and roasting a filter cake for 3 hours at 300 ℃ and 50% of water vapor to obtain the phosphorus-rare earth modified molecular sieve; mixing and pulping the phosphorus rare earth modified molecular sieve, 2 kg of deionized water and 2 g of magnesium sulfate (calculated by magnesium), adjusting the pH value to 5.7, reacting for 3 hours at 60 ℃, filtering and washing to obtain the rare earth, phosphorus and magnesium composite modified molecular sieve Y3.
Preparation of acid-modified clay:
300 g of halloysite calcined at 850 ℃ for 3 hours and 200 g of kaolin calcined at 580 ℃ for 2 hours are taken, 1500 g of deionized water is used for pulping, 50 g of concentrated nitric acid is added, and the mixture reacts at 90 ℃ for 1 hour to obtain the acid modified clay N3.
Preparing a catalyst:
adding 2000 g of deionized water, 120 g of aluminum sol dry basis, 160 g of pseudo-boehmite dry basis, 1200 g of acid modified clay N3 dry basis, 104 g of rare earth, phosphorus and magnesium modified molecular sieve Y3 dry basis and 416 g of REY dry basis into a reaction kettle, pulping for 60 minutes, uniformly stirring, and spray drying to obtain the FCC catalyst which is marked as C3 and prepared by the method.
Example 4
Preparing a rare earth, phosphorus and magnesium modified Y-type molecular sieve:
pulping 1000 g of NaY molecular sieve (dry basis) by using 20 kg of deionized water, adding 110 g of ammonium nitrate and 40 g of ammonium bisulfate, adjusting the pH value to 5.8, exchanging at 130 ℃ for 0.5 hour, filtering, washing by using water, mixing a filter cake with 50 g of lanthanum nitrate (calculated by rare earth oxide), and roasting at 550 ℃ for 1.5 hours to obtain the rare earth modified molecular sieve; pulping the roasted sample obtained by the previous step with 5 kg of deionized water, adding 8 g of diammonium hydrogen phosphate (calculated by phosphorus), adjusting the pH value to 4.2, exchanging for 1.5 hours at 80 ℃, filtering and washing, and roasting a filter cake for 2 hours at 500 ℃ to obtain the phosphorus-rare earth modified molecular sieve; mixing and pulping the phosphorus rare earth modified molecular sieve with 3 kg of deionized water, 2 g of magnesium nitrate and 2 g of magnesium sulfate (calculated as magnesium), adjusting the pH value to 4.2, reacting for 1 hour at 90 ℃, filtering and washing to obtain the rare earth, phosphorus and magnesium composite modified molecular sieve Y4.
Preparing a catalyst:
adding 2000 g of deionized water, 80 g of dried alumina sol, 320 g of dried silica sol, 500 g of dried pseudo-boehmite, 600 g of dried kaolin, 100 g of dried halloysite, 240 g of dried Y4 of the rare earth-phosphorus-magnesium modified molecular sieve and 60 g of dried ZSM-5 into a reaction kettle, pulping for 60 minutes, uniformly stirring, and spray drying to obtain the FCC catalyst which is marked as C4 and prepared by the method.
Comparative example 1
Prepared according to the method provided by patent CN 103084200A: adding 5000 g of NaY molecular sieve and 4000 g of deionized water in a reaction kettle on a dry basis, slowly adding 150 g of lanthanum chloride (in terms of rare earth) under vigorous stirring, adjusting the pH value to 3.5 by using 4 wt% of dilute hydrochloric acid, heating to 90 ℃, stirring for 1.5 hours, filtering, washing and drying; then roasting for 2 hours at 650 ℃ in the atmosphere of 100 percent of water vapor to prepare the rare earth sodium Y molecular sieve with twice once cross.
Putting 2000 g of the prepared rare earth sodium Y molecular sieve dry basis into a reaction kettle, adding 1600 g of deionized water, slowly adding 30 g of lanthanum chloride, 32 g of ferric nitrate, 0.3 g of copper chloride and 50 g of ammonium dihydrogen phosphate under a violent stirring state, adjusting the pH value of the system to be 3.5 by using 4% diluted hydrochloric acid, heating to 90 ℃, stirring for 1 hour, filtering, washing and drying to obtain the rare earth, iron, copper and phosphorus modified molecular sieve DY-1.
Preparation of catalytic cracking catalyst:
adding 2000 g of deionized water and 400 g of pseudo-boehmite dry basis into a reaction kettle, adding 80 g of hydrochloric acid with the concentration of 36 weight percent into the obtained slurry, heating to 65 ℃, acidifying for 1 hour, respectively adding 600 g of kaolin and 200 g of alumina sol dry basis, stirring for 20 minutes, adding 650 g of rare earth, iron, copper and phosphorus modified molecular sieve DY-1 dry basis and 70 g of USY dry basis, pulping for 60 minutes, uniformly stirring, and spray drying to obtain the microspherical catalyst. Roasting the microspherical catalyst at 500 ℃ for 1 hour, washing the microspherical catalyst with ammonium sulfate at 60 ℃ until the content of sodium oxide is less than 0.25 weight percent, finally leaching the microspherical catalyst with 10 times of deionized water, filtering the microspherical catalyst, and drying the microspherical catalyst at 110 ℃ to obtain a comparative FCC catalyst, which is marked as D1.
Comparative example 2
Preparing a modified Y-type molecular sieve:
1000 g of the rare earth modified molecular sieve sample obtained in example 1 was subjected to roasting, and the sample was slurried with 13 kg of deionized water, 50 g of diammonium hydrogen phosphate (in terms of phosphorus) and 20 g of magnesium chloride (in terms of magnesium) were added, exchanged at 80 ℃ for 1 hour, filtered and washed with water, and then the filter cake was subjected to roasting at 600 ℃ for 1 hour to obtain a molecular sieve sample DY-2.
Preparing a catalyst:
adding 2000 g of deionized water, 80 g of rare earth solution dry basis, 200 g of aluminum sol dry basis, 400 g of pseudo-boehmite dry basis, 600 g of the acid modified clay N1 dry basis, 650 g of the modified molecular sieve DY-2 dry basis and 70 g of USY dry basis into a reaction kettle, pulping for 60 minutes, uniformly stirring, and spray drying to obtain the FCC catalyst which is marked as D2 and prepared by the method.
Comparative example 3
Preparing a modified Y-type molecular sieve:
1000 g of a sample roasted by the rare earth modified molecular sieve in the example 1 is pulped by 8 kg of deionized water, 20 g of magnesium chloride (calculated by magnesium) is added, the pH value is adjusted to 3.8, the reaction is carried out for 1 hour at the temperature of 95 ℃, and the mixture is filtered and washed; pulping the obtained rare earth and magnesium modified molecular sieve filter cake with 5 kg of deionized water, adding 50 g of diammonium hydrogen phosphate (calculated by phosphorus), adjusting the pH value to 4.0, exchanging for 1 hour at 80 ℃, filtering, washing with water, and roasting the filter cake for 1 hour at 600 ℃ to obtain a molecular sieve sample DY-3.
Preparing a catalyst:
adding 2000 g of deionized water, 80 g of rare earth solution dry basis, 200 g of aluminum sol dry basis, 400 g of pseudo-boehmite dry basis, 600 g of the acid modified clay N1 dry basis, 650 g of the modified molecular sieve DY-3 dry basis and 70 g of USY dry basis into a reaction kettle, pulping for 60 minutes, uniformly stirring, and spray drying to obtain the FCC catalyst which is marked as D3 and prepared by the method.
The results of evaluating the reaction properties of the catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2 catalyst fixed bed evaluation results
Catalyst and process for preparing same C1 C2 C3 C4 D1 D2 D3
Dry gas 3.52 3.59 3.5 3.37 3.55 3.36 3.17
Liquefied gas 13.75 13.89 13.57 14.91 13.78 12.91 12.33
Gasoline (gasoline) 42.98 43.65 42.63 41.58 41.06 39.17 38.77
Diesel oil 27.42 26.52 27.76 27.61 27.75 25.2 24.81
Heavy oil 5.04 4.97 5.38 5.59 5.91 12.27 14.09
Coke 7.29 7.38 7.16 6.94 7.95 7.09 6.83
Conversion rate 67.54 68.51 66.86 66.8 66.34 62.53 61.1
Total liquid yield 84.15 84.06 83.96 84.1 82.59 77.28 75.91
From the fixed bed evaluation results, the catalyst prepared by the method has lower heavy oil yield under the condition of blending 30% of coker gas oil, and the catalyst prepared by the method has good coker gas oil conversion capability. Compared with the catalyst of comparative example 2 (D2) and the catalyst of comparative example 3 (D3), the heavy oil yield of the catalyst prepared by the method of the invention is greatly reduced, which shows that the modification sequence of phosphorus and magnesium elements has important influence on the performance of the catalyst in the modification process of the molecular sieve. The simultaneous introduction of phosphorus and magnesium elements in the molecular sieve modification process or the introduction of the magnesium element first and then the phosphorus element cannot simultaneously achieve the dual purposes of high heavy oil conversion capacity and good coke selectivity. The catalyst prepared by the method of the present invention has more excellent coke selectivity with increased conversion and decreased heavy oil compared to the catalyst of comparative example 1 (D1).
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (28)

1. The preparation method of the catalytic cracking catalyst for the cracked coker gas oil is characterized by comprising the following steps of: (1) preparing a rare earth, phosphorus and magnesium composite modified Y-type molecular sieve: (a) carrying out ion exchange on the NaY molecular sieve and an ammonium salt solution, filtering, washing, mixing a washed filter cake with rare earth salt, and then roasting for 1-3 hours at the temperature of 400 ℃ and 700 ℃ under 1-50% of water vapor to obtain the rare earth modified Y-type molecular sieve; (b) performing ion exchange on the rare earth modified Y-type molecular sieve obtained in the step (a) and a phosphorus-containing compound or a mixed solution of the phosphorus-containing compound and an ammonium salt, filtering, washing, and roasting for 0.5-3 hours at the temperature of 600 ℃ and under the condition of l% -100% of water vapor to obtain the rare earth and phosphorus composite modified Y-type molecular sieve; (c) performing ion exchange on the Y-shaped molecular sieve compositely modified by the rare earth and the phosphorus obtained in the step (b) and magnesium salt, and then filtering and washing to obtain the Y-shaped molecular sieve compositely modified by the rare earth, the phosphorus and the magnesium; (2) preparing a catalyst: mixing and pulping the molecular sieve, the clay, the pseudo-boehmite and the binder, and then sequentially carrying out spray drying, washing, filtering and drying to prepare the catalytic cracking catalyst for the cracked coker gas oil.
2. The method according to claim 1, wherein the ion exchange in step (a) in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in step (1) is performed according to ammonium salt: NaY molecular sieve: mixing ammonium salt, NaY molecular sieve and deionized water according to the weight ratio of 0.15-1: l:1-50, pulping uniformly, regulating pH value of pulp to 2.0-6.0, and exchanging at 40-130 deg.C for 0.5-4 hr.
3. The method according to claim 1 or 2, wherein the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1) is prepared by ion exchange according to ammonium salt: NaY molecular sieve: mixing ammonium salt, NaY molecular sieve and deionized water according to the weight ratio of 0.2-0.5:1:2-30, pulping uniformly, regulating pH value of the pulp to 3.0-5.0, and exchanging for 1-3 hours at 60-90 ℃.
4. The preparation method according to claim 1, wherein the washed filter cake prepared by the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1) is mixed with a rare earth salt according to the weight ratio of the rare earth salt: NaY molecular sieve 0.001-0.2 ═ l, the rare earth salt is RE2O3And (6) counting.
5. The preparation method according to claim 1 or 4, characterized in that the washed filter cake prepared by the rare earth, phosphorus and magnesium modified Y-type molecular sieve in the step (1) is mixed with a rare earth salt according to the weight ratio of the rare earth salt: NaY molecular sieve is 0.02-0.2:1, and the rare earth salt is RE2O3And (6) counting.
6. The method according to claim 1, wherein the ion exchange in step (b) in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in step (1) is performed according to a phosphorus-containing compound: ammonium salt: NaY molecular sieve: mixing and pulping a phosphorus-containing compound, ammonium salt, a NaY molecular sieve and deionized water uniformly according to the weight ratio of 0.001-0.1:0-0.3:1:1-50, adjusting the pH value of the pulp to 2.0-6.0, and exchanging for 0.5-3 hours at the temperature of 40-130 ℃, wherein the phosphorus-containing compound is counted by P.
7. The method according to claim 1 or 6, wherein the ion exchange in step (b) in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in step (1) is performed according to the following phosphorus-containing compound: ammonium salt: NaY molecular sieve: mixing and pulping a phosphorus-containing compound, ammonium salt, a NaY molecular sieve and deionized water uniformly according to the weight ratio of 0.005-0.04:0-0.2:1:2-30, adjusting the pH value of the pulp to 3.0-5.0, and exchanging for 1-2 hours at 60-90 ℃, wherein the phosphorus-containing compound is counted by P.
8. The method according to claim 1, wherein the ion exchange in step (c) in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in step (1) is carried out according to the ratio of magnesium salt: NaY molecular sieve: mixing magnesium salt, NaY molecular sieve and deionized water according to the weight ratio of 0.001-0.05:1:1-50, pulping uniformly, adjusting the pH value of the pulp to 2.0-6.0, and exchanging at 60-150 ℃ for 0.5-3 hours, wherein the magnesium salt is calculated by Mg.
9. The method according to claim 1 or 8, wherein the ion exchange in step (c) in the preparation of the rare earth, phosphorus and magnesium modified Y-type molecular sieve in step (1) is performed according to the ratio of magnesium salt: NaY molecular sieve: mixing magnesium salt, NaY molecular sieve and deionized water according to the weight ratio of 0.003-0.03:1:2-20, pulping uniformly, adjusting the pH value of the pulp to 3.0-5.0, and exchanging at 70-100 ℃ for 1-2 hours, wherein the magnesium salt is calculated by Mg.
10. The method according to claim 1, wherein the ammonium salt is one or more selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium oxalate and ammonium phosphate.
11. The preparation method according to claim 1 or 4, wherein the rare earth salt is one or more of chloride, nitrate and sulfate of rare earth.
12. A process according to claim 1 or 4, wherein the rare earth salt is a chloride of a rare earth, and the rare earth is lanthanum and/or cerium.
13. The method according to claim 1, wherein the phosphorus compound is one or more selected from the group consisting of orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and pyrophosphoric acid.
14. The preparation method according to claim 1, wherein the magnesium salt is one or more selected from magnesium chloride, magnesium nitrate, magnesium hydroxychloride and magnesium sulfate.
15. The process according to claim 1 or 14, wherein the magnesium salt is magnesium chloride.
16. The preparation method of claim 1, wherein the molecular sieve comprises a rare earth, phosphorus and magnesium composite modified Y-type molecular sieve and a conventional molecular sieve.
17. The preparation method of claim 1 or 16, wherein the rare earth, phosphorus and magnesium composite modified Y-type molecular sieve contains 2-20 wt% of rare earth calculated as rare earth oxide, 0.1-10 wt% of phosphorus calculated as phosphorus, 0.1-5 wt% of magnesium calculated as magnesium, and 0.05-1.0 wt% of sodium oxide calculated as sodium.
18. The method of claim 16, wherein the conventional molecular sieve is one or a mixture of conventional modified Y-zeolite, ZSM zeolite, beta zeolite, omega zeolite, MCM zeolite, SAPO zeolite.
19. The preparation method as claimed in claim 18, wherein the conventional modified Y-type zeolite is HY, NH4Y, REY, USY, REUSY or mixtures thereof.
20. The method of claim 1 or 16, wherein the molecular sieve comprises 20-100 wt% of the Y-type molecular sieve compositely modified with rare earth, phosphorus and magnesium, and 0-80 wt% of conventional molecular sieve, based on the dry weight.
21. The method according to claim 1, wherein the clay is kaolin, sepiolite, halloysite, montmorillonite or an acid-modified clay thereof.
22. The method of claim 1 or 21, wherein the clay is an acid-modified kaolin, an acid-modified halloysite, or a mixture thereof.
23. The method as claimed in claim 22, wherein the acid modification process comprises calcining the clay at 600-1000 ℃ for 1-5h, and then adding the clay: water: the mass ratio of concentrated hydrochloric acid or concentrated nitric acid is 1:3-10:0.05-2, and the acid modified clay is prepared after the reaction for 1-6 hours at the constant temperature of 60-90 ℃.
24. The method of claim 1, wherein the pseudoboehmite is one of boehmite, gibbsite, and bayer stone, or a combination thereof.
25. The method of claim 1 or 24, wherein the pseudoboehmite is boehmite.
26. The preparation method according to claim 1, wherein the binder is one of aluminum sol, aluminum chlorohydrate and silica sol or a mixture thereof.
27. The catalytic cracking catalyst for cracked coker gas oil prepared by the preparation method of claim 1, wherein the catalytic cracking catalyst comprises 15-70 wt% of molecular sieve, 15-60 wt% of clay, 8-30 wt% of pseudo-boehmite and 3-20 wt% of binder, based on the mass of the catalyst on a dry basis.
28. The catalytic cracking catalyst for cracked coker gas oil as claimed in claim 27, wherein the catalyst contains 0-8 wt% of rare earth metal oxide, and the rare earth element in the rare earth metal oxide is selected from one or a combination of La, Ce, Pr and Nd.
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