CN113355126A - Crude oil catalytic cracking method - Google Patents

Crude oil catalytic cracking method Download PDF

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Publication number
CN113355126A
CN113355126A CN202110694442.0A CN202110694442A CN113355126A CN 113355126 A CN113355126 A CN 113355126A CN 202110694442 A CN202110694442 A CN 202110694442A CN 113355126 A CN113355126 A CN 113355126A
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parts
catalyst
molecular sieve
water
carbonate
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Inventor
施宗波
卓润生
刘新生
张青
李邵红
钟嘉兴
胡泽松
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Runhe Catalytic Materials Zhejiang Co Ltd
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Runhe Catalytic Materials Zhejiang Co Ltd
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    • 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
    • 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
    • B01J29/80—Mixtures of different zeolites
    • B01J35/615—
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J29/084—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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively

Abstract

The invention discloses a crude oil catalytic cracking method, which comprises the following steps: (1) preparing a low-bulk-ratio catalytic cracking component from raw materials such as a Y molecular sieve, macroporous alumina and the like; (2) preparing a catalytic cracking component with high bulk ratio by using a P-ZSM-5 molecular sieve and the like. The catalyst is suitable for a down-flow catalytic cracking process, heavy component oil and light component oil can be selectively cracked by the method, the method is suitable for the catalytic cracking process of crude oil with wide distillation range and high heavy metal content, the content of byproducts such as coke, dry gas and the like in a cracked product is low, the yield of low-carbon olefin is high, and the consumption cost of the catalyst is low.

Description

Crude oil catalytic cracking method
Technical Field
The invention relates to the field of petroleum processing, in particular to a crude oil catalytic cracking method.
Background
Crude oil is a complex mixture of many hydrocarbons. At present, oil refineries mainly convert crude oil into fuels such as gasoline, kerosene and diesel oil, and meanwhile, petrochemical products such as low-carbon alkanes are by-produced. The low-carbon olefin is generally referred to as unsaturated hydrocarbon with four or less carbon atoms, and mainly comprises organic chemical raw materials with high economic value, such as ethylene, propylene, butadiene and the like, wherein the propylene is an important chemical raw material, is mainly used for producing polypropylene, acrylonitrile, acrylic acid, acrolein and the like, and is a basic raw material of three synthetic materials (plastics, rubber and fibers). With the development of economy in China, the demand of the organic chemical raw materials is increased year by year, and although the production scale of the low-carbon olefin is also increased year by year, the increased demand cannot be met, so that the low-carbon alkane can be effectively utilized, and the method not only meets the national low-carbon environmental protection policy and the circular economy concept, but also has good economic benefit and social benefit.
The traditional crude oil processing needs to be carried out through processes of atmospheric and vacuum treatment, hydrotreating, catalytic cracking or catalytic cracking and the like, and the processes have long process flow, large investment and high energy consumption. In order to solve the problems of long process flow, large investment and high energy consumption of the direct catalytic cracking technology of crude oil, various direct cracking technologies and catalysts of crude oil exist at present, and patent CN112745914A discloses an integrated method and an integrated device for converting crude oil into petrochemical products, wherein the integrated method mainly comprises the following steps: carrying out flash separation on crude oil to obtain a light component, a medium component and a heavy component, and then respectively cracking light oil and heavy oil, wherein the method has relatively more equipment and complex reaction process; patent CN111718231A discloses a method for producing ethylene and propylene by direct catalytic conversion of crude oil, which uses different catalysts for light oil and heavy oil, the light oil is catalyzed by Y and ZSM-5 molecular sieves as main active components, the heavy oil is catalyzed by a catalyst with a mixture of multiple molecular sieves as main active components, the steps are complicated, and the light oil and the heavy oil cannot be catalytically cracked simultaneously.
Disclosure of Invention
In order to solve the technical problems, the invention provides a crude oil catalytic cracking method, which can simultaneously crack crude oil containing light oil and heavy oil, and has high crude oil cracking conversion rate and high low-carbon olefin yield.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a crude oil catalytic cracking method, which comprises the following steps:
(1) mixing clay, a binder, water, carbonate and an aluminum compound to carry out gelling reaction;
(2) mixing the slurry after the gelling reaction with the molecular sieve slurry 1, homogenizing and roasting to obtain a catalyst A;
(3) mixing the slurry after the gelling reaction with the molecular sieve slurry 2, homogenizing and roasting to obtain a catalyst B;
(4) mixing the catalyst A, B, and carrying out catalytic cracking on crude oil after passivation treatment;
catalyst a is a low bulk ratio catalytic cracking component, having a bulk density less than <0.7 g/cc; the catalyst B is a high bulk ratio catalytic cracking component and has a bulk density of less than >0.8 g/cc.
Bulk density of catalyst B-bulk density of catalyst a >0.15 g/cc. The invention does not limit the sequence of (2) and (3), and the catalyst A in (2) and the catalyst B in (3) can be obtained after (1) gelling reaction, or the catalyst B in (3) and the catalyst A in (2) can be obtained after (1) gelling reaction.
In some embodiments, the clay is selected from one or more of kaolin, montmorillonite, bentonite, preferably kaolin;
the binder is selected from one of aluminum sol and silica sol, and is preferably aluminum sol;
the carbonate is selected from one of lanthanum carbonate, cerium carbonate, praseodymium carbonate, yttrium carbonate and zirconium carbonate;
the aluminum compound is selected from one or more of pseudo-boehmite, alumina, hydrated alumina, macroporous alumina and aluminum hydroxide, and is preferably pseudo-boehmite; more preferably, it is a small-pore pseudo-boehmite.
In some embodiments, the (1) comprises the following raw materials in parts by weight: 2.5-6 parts of clay, 0.5-2 parts of binder, 0-0.3 part of carbonate, 3-8 parts of water and 1-4 parts of aluminum compound;
further, (1) comprises the following raw materials in parts by weight: 3.1 to 5.4 parts of clay, 0.8 to 1.6 parts of binder, 0 to 0.1 part of carbonate, 3.5 to 7 parts of water and 1 to 3.1 parts of aluminum compound.
In some embodiments, the pH value of the mixed solution of the clay, the binder, the water and the aluminum compound is 2.5-3.5.
If the pH value of the mixed solution is not within the range of 2.5-3.5, the pH value can be adjusted by using a reagent, and the used reagent does not influence the cracking performance of crude oil.
In some embodiments, molecular sieve slurry 1 comprises the following components in parts by weight: 0.2-1 part of aluminum compound, 1-3 parts of Y-type molecular sieve and 2.5-5 parts of water;
further, the composition comprises the following components in parts by weight: 0.5-1 part of aluminum compound, 1.2-2.4 parts of Y-type molecular sieve and 3-4.5 parts of water;
further, the composition comprises the following components in parts by weight: 0.5 part of aluminum compound, 1.2-2.4 parts of Y-type molecular sieve and 3-4.5 parts of water.
In some embodiments, the aluminum compound is selected from one or more of pseudo-boehmite, alumina, hydrated alumina, macroporous alumina and aluminum hydroxide, and is preferably pseudo-boehmite; more preferably macroporous pseudo-boehmite;
further, the specific surface area of the large-pore pseudo-boehmite is 170-200 m2(ii)/g, the most probable pore diameter is 15-16 nm, and the pore volume is 1-1.5 g/cc;
the Y-type molecular sieve is selected from one or more of REUSY type, USY type and REY type molecular sieves.
The Y-type molecular sieve adopted by the invention is rich in mesopores and macropores, has large pore volume and small bulk density, has slow descending speed after entering the lifting pipe, and is suitable for heavy oil components in cracked crude oil. In addition, the catalyst A is added with heavy metal resistant components, has relatively large abrasion index, can absorb metals such as V, Ni and the like in heavy oil in the reaction process and can be crushed in a certain time so as to reduce the content of heavy metals in the catalyst.
In some embodiments, molecular sieve slurry 2 comprises the following components in parts by weight: 1-6 parts of modified molecular sieve and 4-10 parts of water;
further, the composition comprises the following components in parts by weight: 2-4 parts of modified molecular sieve and 6 parts of water.
Further, the modified molecular sieve is selected from a phosphorus modified molecular sieve and a rare earth modified molecular sieve; preferably a phosphorus modified molecular sieve; further is a P-ZSM-5 molecular sieve.
The P-ZSM-5 molecular sieve adopted by the invention has small size of sieve pores and large bulk density, has high descending speed after entering the riser, is suitable for light oil components in cracked crude oil and light oil components produced by secondary reaction, has less heavy metal enrichment, long reaction life, relatively smaller catalyst abrasion index and longer average residence time in the device.
In some embodiments, the difference in bulk density of the catalysts A, B1, 2 is >0.15 g/cc.
The invention uses the mixed catalyst with different densities, heavy components in the crude oil react in the catalyst A with small density, rich mesopores and macropores and strong cracking activity, light components in the crude oil and cracked light component oil react in the catalyst B with high density and strong cracking activity, and the respective reactions of heavy oil and light oil are matched, so that the steps of the thermal cracking reaction of the heavy component oil are reduced, the cracking conversion rate and the yield of low-carbon alkane are improved, and the yields of coke and dry gas except ethylene are reduced.
In some embodiments, the roasting temperature in (2) and (3) is 450-600 ℃, the time is 2-4 h, preferably the temperature is 500 ℃, and the time is 3 h;
(4) the catalyst A: the mass ratio of B is 1: 1-5, and the preferred mass ratio is 1: 3.
The invention cracks crude oil through the density difference of the catalyst, so that the heavy oil with low density component selectivity is subjected to catalytic cracking reaction, and the heavy oil with high density component selectivity is subjected to catalytic cracking reaction. The carbon capacity of the cracking catalyst is improved, the cracking activity of the cracking catalyst is improved, the coking of heavy oil on the surface of the high-density catalyst is reduced, and the utilization efficiency of cracking components is improved.
The catalyst in the traditional device is the same catalyst, the distribution of the catalyst in different sections is the same (the catalyst is uniformly distributed in the device), the concentration of the low-density catalytic cracking catalyst at the top end of the reactor is high, the concentration of the high-density catalytic cracking catalyst at the lower end of the reactor is high, and the gradient distribution in the device is utilized to ensure that crude oil is subjected to the cracking process firstly and then subjected to the cracking process by utilizing the difference of the catalyst density, so that the benefit efficiency of cracking and cracking components is improved, the cracking catalyst is reduced to be used in the cracking process, and the cracking catalyst is used in the cracking process.
The invention has the following beneficial effects:
(1) the method of the invention uses the catalyst with different density to catalytically crack the crude oil, so that the cracking conversion rate of the crude oil is obviously improved, the yield of coke and dry gas except ethylene is reduced, and the yield of ethylene, propylene and butylene is improved.
(2) The catalyst of the invention is used for a single lifting pipe, and compared with a multi-section reaction, the catalyst has the advantages of multiple lifting pipes, less investment, low energy consumption in the running process and easy operation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
In the embodiment of the invention, the specific surface area of the sample is measured by adopting a BET low-temperature nitrogen adsorption method, and the wear index of the sample is measured by a wear index analyzer.
The catalysts in the comparative example and the example are respectively soaked in 4000ppm V and 2000ppm Ni, and then aged for 10 hours by 100 wt% steam at 810 ℃, and the catalytic cracking reaction of crude oil is evaluated on a miniature descending fluidized bed reactor. The experiment is carried out by desalted Kazakhstan crude oil, the catalyst inventory of the reverse regeneration system is 20 kg, the crude oil is predicted to be 300 ℃, the outlet temperature of a riser is 630 ℃, the regeneration temperature of the catalyst is 750 ℃, and the retention time is 1.2 seconds. And (3) after the reaction, performing secondary cooling on the high-temperature oil gas to obtain a gas phase product and a liquid phase product, and evaluating the gas and the liquid on a matched gas chromatography. For other measurements such as bulk density, see (national Standard for testing methods for Petroleum and Petroleum products, published in 1989 by Chinese standards Press).
Comparative example 1
Under the stirring condition, 3.6 kg (dry basis) of kaolin and 1.0 kg (dry basis) of alumina sol are added into 3.5 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 1.8 kg (dry basis) of small-pore pseudo-boehmite (the specific surface area is 234m2/g, the most probable pore diameter is 3.4nm, the pore volume is 0.34g/cc, the same applies below) is added, and the pH of the slurry is adjusted to 2.5-3.5 through HCl, so that the small-pore pseudo-boehmite generates gelling reaction. After stirring for 30 minutes, 0.6 kg (dry basis) of REUSY molecular sieve (SiO2/Al2O3 molar ratio 5.4, RE2O3The content of 2.1 wt%) 3 kg (dry basis) of P-ZSM-5 molecular sieve (SiO2/Al2O3 molar ratio is 27, P2O5 content is 2.5 wt%) and 6 kg of water, continuously pulping for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst R1.
The bulk ratio of the catalyst R1 was 0.72g/cc, the attrition index was 1.9 wt%/h, and the specific surface area was 205m 2/g. The catalyst R1 is used for crude oil catalytic cracking after being passivated by metal and water vapor.
Comparative example 2
Under the stirring condition, 5.4 kg (dry basis) of kaolin and 1.0 kg (dry basis) of alumina sol are added into 3.5 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 1.8 kg (dry basis) of small-hole pseudoboehmite is added, and the pH value of the slurry is adjusted to 2.5-3.5 through HCl, so that the small-hole pseudoboehmite generates a gelling reaction. Stirring for 30 minutes, adding molecular sieve slurry consisting of 0.3 kg (dry basis) REUSY molecular sieve and 1.5 kg (dry basis) P-ZSM-5 molecular sieve, continuing pulping for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst R2.
The bulk ratio of the catalyst R2 was 0.81g/cc, the attrition index was 1.0 wt%/h, and the specific surface area was 145m 2/g. The catalyst R2 is used for crude oil catalytic cracking after being passivated by metal and water vapor.
Example 1
Under the stirring condition, 3.2 kg (dry basis) of kaolin and 0.8 kg (dry basis) of alumina sol are added into 7 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 3.1 kg (dry basis) of small-hole pseudoboehmite is added, and the pH value of the slurry is adjusted to 2.5-3.5 through HCl, so that the small-hole pseudoboehmite is subjected to a gelling reaction. After stirring for 30 minutes, adding molecular sieve slurry consisting of 0.5 kg of macroporous boehmite (specific surface area 186m2/g, most probable pore diameter 15.6nm, pore volume 1.07g/cc), 2.4 kg (dry basis) of REUSY molecular sieve and 4.5 kg of water, continuing beating for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst A.
Under the stirring condition, 3.4 kg (dry basis) of kaolin and 1.6 kg (dry basis) of alumina sol are added into 3.5 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 1 kg (dry basis) of small-hole pseudo-boehmite is added, the pH value of the slurry is adjusted to 2.5-3.5 through HCl, and the small-hole pseudo-boehmite is subjected to a gelling reaction. Stirring for 30 minutes, adding molecular sieve slurry consisting of 4 kg (dry basis) of P-ZSM-5 molecular sieve and 6 kg of water, continuing pulping for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst B.
The bulk ratio of catalyst A was 0.63g/cc, the attrition index was 4.3 wt%/h, and the specific surface area was 213m 2/g.
The bulk ratio of catalyst B was 0.84g/cc, the attrition index was 1.1 wt%/h, and the specific surface area was 215m 2/g.
Catalyst A and catalyst B were mixed by mass 1:3 to obtain the mixed catalyst, and performing metal and steam passivation treatment to the mixed catalyst for catalytic cracking of crude oil.
Example 2
Under the stirring condition, 4.5 kg (dry basis) of kaolin and 0.8 kg (dry basis) of alumina sol are added into 3.5 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 3 kg (dry basis) of small-pore pseudo-boehmite is added, the pH value of the slurry is adjusted to 2.5-3.5 through HCl, and the small-pore pseudo-boehmite is subjected to a gelling reaction. Stirring for 30 minutes, adding a molecular sieve slurry consisting of 0.5 kg of macroporous boehmite, 1.2 kg (dry basis) of REUSY molecular sieve and 3 kg of water, continuing pulping for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst A.
Under the stirring condition, 5.4 kg (dry basis) of kaolin and 1.6 kg (dry basis) of alumina sol are added into 3.5 kg of deionized water, the mixture is stirred at a high speed for 1 hour, 1 kg (dry basis) of small-hole pseudoboehmite is added after the kaolin is completely dispersed in the slurry, and the pH value of the slurry is adjusted to 2.5-3.5 through HCl so that the small-hole pseudoboehmite generates a gelling reaction. Stirring for 30 minutes, adding molecular sieve slurry consisting of 2 kg (dry basis) of P-ZSM-5 molecular sieve and 6 kg of water, continuing pulping for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst B.
The bulk ratio of catalyst A was 0.67g/cc, the attrition index was 3.7 wt%/h, and the specific surface area was 156m 2/g.
The bulk ratio of catalyst B was 0.84g/cc, the attrition index was 1.1 wt%/h, and the specific surface area was 134m 2/g.
Catalyst A and catalyst B were mixed by mass 1:3 to obtain the mixed catalyst, and performing metal and steam passivation treatment to the mixed catalyst for catalytic cracking of crude oil.
Example 3
Under the stirring condition, 3.1 kg (dry basis) of kaolin, 0.1 kg of lanthanum carbonate and 0.8 kg (dry basis) of alumina sol are added into 7 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 3.1 kg (dry basis) of small-hole pseudoboehmite is added, the pH of the slurry is adjusted to 2.5-3.5 through HCl, and the small-hole pseudoboehmite is subjected to a gelling reaction. After stirring for 30 minutes, adding molecular sieve slurry consisting of 0.5 kg of macroporous boehmite (specific surface area 186m2/g, most probable pore diameter 15.6nm, pore volume 1.07g/cc), 2.4 kg (dry basis) of REUSY molecular sieve and 4.5 kg of water, continuing beating for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst A.
Under the stirring condition, 3.4 kg (dry basis) of kaolin and 1.6 kg (dry basis) of alumina sol are added into 3.5 kg of deionized water, the mixture is stirred at a high speed for 1 hour, after the kaolin is completely dispersed in the slurry, 1 kg (dry basis) of small-hole pseudo-boehmite is added, the pH value of the slurry is adjusted to 2.5-3.5 through HCl, and the small-hole pseudo-boehmite is subjected to a gelling reaction. Stirring for 30 minutes, adding molecular sieve slurry consisting of 4 kg (dry basis) of P-ZSM-5 molecular sieve and 6 kg of water, continuing pulping for 30 minutes, homogenizing, spray-forming, and roasting at 500 ℃ for 3 hours to obtain the catalyst B.
The bulk ratio of catalyst A was 0.64g/cc, the attrition index was 4.8 wt%/h, and the specific surface area was 210m 2/g.
The bulk ratio of catalyst B was 0.84g/cc, the attrition index was 1.1 wt%/h, and the specific surface area was 215m 2/g.
Catalyst A and catalyst B were mixed by mass 1:3 to obtain the mixed catalyst, and performing metal and steam passivation treatment to the mixed catalyst for catalytic cracking of crude oil.
The cracking performance in the crude oil catalytic cracking process in comparative examples 1-2 and examples 1-3 was tested, and the test results are shown in the following table:
Figure BDA0003127507270000071
the REY molecular sieve and the P-ZSM-5 molecular sieve of comparative example 1 and example 1 have the same total content, and it is understood from the results of comparative example 1 and example 1 that the crude oil cracking conversion is remarkably improved, the dry gas yield of coke and other than ethylene is reduced, and ethylene, the yield of propylene and butylene is improved, a mixed catalyst with different densities is used on the surface, heavy components in crude oil are firstly reacted in a catalyst with small density, rich mesopores and macropores and strong cracking activity, light components in the crude oil and cracked light component oil are reacted in a catalyst with large density and strong cracking activity, and the respective reactions of heavy oil and light oil are matched, so that the steps of thermal cracking reaction of the heavy component oil are reduced, the cracking conversion rate and the triene yield are improved, and the yields of coke and dry gas except ethylene are reduced.
From the results of comparative example 1 and comparative example 2, it can be seen that the reduction of the molecular sieve content and the reduction of the cracking conversion rate are large. From the results of examples 1 and 2, it is clear that the molecular sieve content is reduced and the cracking conversion rate is reduced by using the two agents with different densities.
From the results of examples 2 and 3, it is understood that the addition of yttrium carbonate to the catalyst contributes to an increase in the cracking conversion, a decrease in the yield of coke and dry gas other than ethylene, and an increase in the yield of triene.
Therefore, the invention uses Y, ZSM-5 molecular sieve to prepare two catalysts with different densities, and has better cracking effect on crude oil.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the present invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A crude oil catalytic cracking method is characterized by comprising the following steps:
(1) mixing clay, a binder, water, carbonate and an aluminum compound to carry out gelling reaction to obtain slurry;
(2) mixing the slurry in the step (1) with the molecular sieve slurry 1, homogenizing and roasting to obtain a catalyst A;
(3) mixing the slurry after the gelling reaction with the molecular sieve slurry 2, homogenizing and roasting to obtain a catalyst B;
(4) mixing the catalyst A, B, and carrying out catalytic cracking on crude oil after passivation treatment;
the bulk density of catalyst a is less than <0.7 g/cc; the bulk density of catalyst B is less than >0.8 g/cc;
bulk density of catalyst B-bulk density of catalyst a >0.15 g/cc.
2. The method according to claim 1, wherein the clay is selected from one or more of kaolin, montmorillonite and bentonite, preferably kaolin;
the binder is selected from one of aluminum sol and silica sol, and is preferably aluminum sol;
the carbonate is selected from one of lanthanum carbonate, cerium carbonate, praseodymium carbonate, yttrium carbonate and zirconium carbonate;
the aluminum compound is selected from one or more of pseudo-boehmite, alumina, hydrated alumina, macroporous alumina and aluminum hydroxide, and is preferably pseudo-boehmite; more preferably, it is a small-pore pseudo-boehmite.
3. The method according to claim 1 or 2, characterized in that (1) comprises the following raw materials in parts by weight: 2.5-6 parts of clay, 0.5-2 parts of binder, 0-0.3 part of carbonate, 3-8 parts of water and 1-4 parts of aluminum compound;
further, (1) comprises the following raw materials in parts by weight: 3.1 to 5.4 parts of clay, 0.8 to 1.6 parts of binder, 0 to 0.1 part of carbonate, 3.5 to 7 parts of water and 1 to 3.1 parts of aluminum compound.
4. The method according to claim 1, wherein the pH value of the mixed solution of clay, binder, water and aluminum compound is 2.5-3.5.
5. The method of claim 1, wherein the molecular sieve slurry 1 comprises the following components in parts by weight: 0.2-1 part of aluminum compound, 1-3 parts of Y-type molecular sieve and 2.5-5 parts of water;
further, the composition comprises the following components in parts by weight: 0.5-1 part of aluminum compound, 1.2-2.4 parts of Y-type molecular sieve and 3-4.5 parts of water;
further, the composition comprises the following components in parts by weight: 0.5 part of aluminum compound, 1.2-2.4 parts of Y-type molecular sieve and 3-4.5 parts of water.
6. The method according to claim 5, wherein the aluminum compound is selected from one or more of pseudo-boehmite, alumina, hydrated alumina, macroporous alumina and aluminum hydroxide, and is preferably pseudo-boehmite; more preferably macroporous pseudo-boehmite;
further, the specific surface area of the large-pore pseudo-boehmite is 170-200 m2(ii)/g, the most probable pore diameter is 15-16 nm, and the pore volume is 1-1.5 g/cc;
the Y-type molecular sieve is selected from one or more of REUSY type, USY type and REY type molecular sieves.
7. The method of claim 1, wherein the molecular sieve slurry 2 comprises the following components in parts by weight: 1-6 parts of modified molecular sieve and 4-10 parts of water;
further, the composition comprises the following components in parts by weight: 2-4 parts of modified molecular sieve and 6 parts of water.
8. The method of claim 7, wherein the modified molecular sieve is selected from the group consisting of phosphorus modified molecular sieves, rare earth modified molecular sieves; preferably a phosphorus modified molecular sieve; further is a P-ZSM-5 molecular sieve.
9. The process of claim 1 wherein the difference in bulk density of the catalyst A, B is >0.15 g/cc.
10. The method according to claim 1, wherein the roasting temperature in (2) and (3) is 450-600 ℃ and the roasting time is 2-4 h, preferably 500 ℃ and the roasting time is 3 h;
(4) the catalyst A: the mass ratio of B is 1: 1-5, and the preferred mass ratio is 1: 3.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1735678A (en) * 2002-12-06 2006-02-15 阿尔伯麦尔荷兰有限公司 Hydro processing of hydrocarbon using a mixture of catalysts
CN105688977A (en) * 2015-12-30 2016-06-22 中国石油天然气股份有限公司 Method for preparing catalytic cracking catalyst containing pseudo-boehmite
CN107828443A (en) * 2016-09-16 2018-03-23 鲁姆斯科技公司 For making the fluidized catalytic cracking method and device of light olefins yields maximization and other application
CN112439462A (en) * 2019-09-02 2021-03-05 中国石油化工股份有限公司 Method for recycling waste hydrogenation catalyst
CN112831341A (en) * 2020-12-30 2021-05-25 润和催化剂股份有限公司 Application of rare earth carbonate directly as vanadium passivator and vanadium resistant catalytic cracking catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1735678A (en) * 2002-12-06 2006-02-15 阿尔伯麦尔荷兰有限公司 Hydro processing of hydrocarbon using a mixture of catalysts
CN105688977A (en) * 2015-12-30 2016-06-22 中国石油天然气股份有限公司 Method for preparing catalytic cracking catalyst containing pseudo-boehmite
CN107828443A (en) * 2016-09-16 2018-03-23 鲁姆斯科技公司 For making the fluidized catalytic cracking method and device of light olefins yields maximization and other application
CN112439462A (en) * 2019-09-02 2021-03-05 中国石油化工股份有限公司 Method for recycling waste hydrogenation catalyst
CN112831341A (en) * 2020-12-30 2021-05-25 润和催化剂股份有限公司 Application of rare earth carbonate directly as vanadium passivator and vanadium resistant catalytic cracking catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
H.斯科特•福格勒, 中国石化出版社 *

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