CN117983283A - Heavy metal resistant catalytic cracking auxiliary agent and preparation method thereof - Google Patents
Heavy metal resistant catalytic cracking auxiliary agent and preparation method thereof Download PDFInfo
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- CN117983283A CN117983283A CN202410409450.XA CN202410409450A CN117983283A CN 117983283 A CN117983283 A CN 117983283A CN 202410409450 A CN202410409450 A CN 202410409450A CN 117983283 A CN117983283 A CN 117983283A
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- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 44
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 60
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 24
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 16
- 239000004005 microsphere Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a heavy metal resistant catalytic cracking auxiliary agent and a preparation method thereof, and relates to the technical field of chemical auxiliary agents. The heavy metal resistant catalytic cracking auxiliary agent consists of a modified molecular sieve, modified kaolin and alumina sol, wherein the modified molecular sieve is obtained by loading La, pr and Co by adopting an HSY molecular sieve, and the modified kaolin is obtained by washing the kaolin with water, modifying by adopting phosphoric acid, presintering and calcining. The invention overcomes the defects of the prior art, effectively improves the catalytic cracking activity of the catalytic auxiliary agent on heavy oil, improves the conversion efficiency of heavy oil and the gasoline yield, and further improves the economic benefit of production.
Description
Technical Field
The invention relates to the technical field of chemical auxiliary agents, in particular to an anti-heavy metal catalytic cracking auxiliary agent and a preparation method thereof.
Background
Catalytic cracking is one of the main methods for secondary deep processing of crude oil, and compared with foreign catalytic cracking raw materials, the method has the advantages that the content of carbon residue, heavy metals and the like in raw oil of many catalytic cracking devices in China is high, and the high-efficiency conversion of heavy oil, the improvement of the yield of target products and the reduction of byproducts are still main targets pursued by the catalytic cracking devices.
The Y molecular sieve is used as an active component of a catalytic cracking catalyst and widely applied to the oil refining industry, has good catalytic cracking performance on light oil, but faces to continuously heavy FCC raw oil, and because the pore canal size of the Y molecular sieve is smaller, the diffusion of heavy oil macromolecules is limited, so that part of active centers in the pore canal of the molecular sieve cannot be effectively utilized, and the efficiency is reduced; in addition, part of the active center of the outer surface of the catalyst is easily covered by coke, and the activity of the catalyst is reduced.
Patent number 202211021180.2 discloses an additive for improving heavy metal pollution resistance of an FCC catalyst, which is prepared by introducing a magnesium-rare earth-aluminum ternary dihydroxy compound secondary structure unit with large specific surface, large pore volume and excellent heavy metal pollution element passivation performance into a clay carrier structure through an acid extraction combined coprecipitation in-situ construction method, and then spray drying and forming the secondary structure unit with a bonding component. And aiming at the characteristic of HSY, the further modification and compounding treatment to obtain the catalytic auxiliary agent with further high performance is a great research direction at the present stage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the heavy metal resistant catalytic cracking auxiliary agent and the preparation method thereof, which effectively improve the catalytic cracking activity of the catalytic auxiliary agent on heavy oil, improve the conversion efficiency of heavy oil and the gasoline yield, and further improve the economic benefit of production.
In order to achieve the above object, the technical scheme of the present invention is realized by the following technical scheme:
The heavy metal resistant catalytic cracking auxiliary agent consists of 25-30 of modified molecular sieve, 42-50 of modified kaolin and 17-20 of alumina sol in mass ratio, wherein the modified molecular sieve is obtained by loading La, pr and Co with equal mass by adopting an HSY molecular sieve, and the total loading amount of La, pr and Co is 0.2-1.2% of the total loading amount of the HSY molecular sieve; the modified kaolin is obtained by washing kaolin with water, modifying with phosphoric acid, presintering and calcining.
Preferably, the specific preparation method of the modified molecular sieve comprises the following steps:
s1-1, preparing a metal salt solution of La, pr and Co;
s1-2, stirring an HSY molecular sieve with deionized water for 20-30min under the environment of the pressure of 2-4Mpa and the temperature of 50-80 ℃, repeatedly carrying out suction filtration for 2-3 times, and then drying to obtain a pretreated HSY molecular sieve;
S1-3, sequentially soaking the pretreated HSY molecular sieve in each metal salt solution, roasting at 480-550 ℃ for 20-40min after single soaking and drying, roasting at 480-550 ℃ for 1-2h after final soaking and drying, and grinding and sieving with a 20-mesh sieve to obtain the modified molecular sieve.
Preferably, the preparation method of the metal salt solution of La, pr and Co in the step S1-1 is to dissolve LaCl3, pr (NO 3) 3 and CoCl2 in deionized water respectively.
Preferably, the pretreatment of the HSY molecular sieve in the step S1-3 is sequentially carried out by immersing the pretreated HSY molecular sieve in a metal salt solution with the temperature of 50-60 ℃ for preliminary drying, and then transferring the HSY molecular sieve into an oven with the temperature of 70-80 ℃ for drying to constant weight.
Preferably, the specific preparation method of the modified kaolin comprises the following steps:
s2-1, repeatedly carrying out suction filtration on kaolin by deionized water for 2-4 times, drying, adding 3% phosphoric acid solution, respectively stirring at the temperature of 0 ℃, 15 ℃ and 35 ℃ for 15-30min, filtering, and washing and filtering by deionized water for 4-5 times to obtain pretreated kaolin;
S2-2, presintering the pretreated kaolin at the temperature of 280-350 ℃ for 1-2 hours, and then adjusting the temperature to 600-800 ℃ for calcining for 1-2 hours to obtain the modified kaolin.
Preferably, the drying in the step S2-1 is performed at 350 ℃ for 1-2 hours.
The preparation method of the heavy metal resistant catalytic cracking auxiliary agent comprises the following steps:
(1) Mixing a modified molecular sieve and modified kaolin, and adding deionized water to prepare a primary slurry;
(2) Treating the primary slurry by adopting liquid nitrogen for 5-10min, taking out the frozen primary slurry, crushing the primary slurry, and sieving the crushed primary slurry by a 20-40-mesh sieve to obtain a pretreated material for later use;
(3) Adding deionized water into the pretreated material mixed aluminum sol, stirring to prepare secondary slurry, pulping, and spray-drying to prepare microspheres for later use;
(4) The microspheres are respectively baked for 30-80min at 300-500 ℃, 600-800 ℃ and 850-900 ℃ and then are sieved by a 20-mesh sieve, thus obtaining the heavy metal resistant catalytic cracking auxiliary agent.
Preferably, the solid content of the primary slurry in the step (1) is 45-65%.
Preferably, the solid content of the secondary slurry in the step (3) is 25-45%.
The invention provides a heavy metal resistant catalytic cracking auxiliary agent and a preparation method thereof, which have the advantages compared with the prior art that:
The application adopts the HSY molecular sieve as an active component of a heavy oil catalytic cracking (RFCC) catalyst, and carries out impregnation and roasting modification on the HSY molecular sieve by adopting La, pr and Co rare earth salts in a stepwise impregnation method to improve the overall activity, so that the heavy oil conversion rate of the heavy metal catalytic cracking auxiliary agent is effectively improved, and the application adopts the kaolin modified by phosphoric acid at the temperature of 0 ℃, 15 ℃ and 35 ℃ to effectively improve the heavy oil conversion rate of the final heavy metal catalytic cracking auxiliary agent, and carries out pulping, roasting and hydrothermal reaction after liquid nitrogen freezing and adhesive mixing, so that the catalytic stability of the catalyst is further improved, the heavy oil catalytic cracking activity of the catalyst is obviously improved, and the product distribution is further improved on the premise of effectively improving the high heavy oil conversion rate, so that the aim of industrial production is fulfilled.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The sources of the raw materials in the following examples and comparative examples are shown in Table 1 below:
TABLE 1
Example 1:
1. The modified molecular sieve is prepared by the following steps:
Respectively dissolving LaCl 3、Pr(NO3)3、CoCl2 in deionized water to prepare LaCl 3 aqueous solution, pr (NO 3) 3 aqueous solution and CoCl 2 aqueous solution;
1. modified molecular sieve a:
(1) Soaking the HSY molecular sieve in a LaCl 3 aqueous solution at 55 ℃ until the water is fully evaporated, and then roasting at 500 ℃ for 30min to obtain a primarily treated HSY molecular sieve;
(2) Soaking the primarily treated HSY molecular sieve in Pr (NO 3)3 water solution at 55 ℃ C., continuously until the water is fully evaporated, and then roasting at 500 ℃ C. For 30min to obtain a secondarily treated HSY molecular sieve;
(3) Soaking the secondarily treated HSY molecular sieve in a CoCl 2 water solution at the temperature of 55 ℃, continuously soaking until the water is fully evaporated, and roasting at the temperature of 500 ℃ for 1.5 hours to obtain a modified molecular sieve A, wherein the total load of La, pr and Co in the modified molecular sieve A is 0.5% of the total load of the HSY molecular sieve.
2. Modified molecular sieve B:
(1) Mixing LaCl 3 aqueous solution, pr (NO 3)3 aqueous solution and CoCl 2 aqueous solution to prepare mixed salt solution;
(2) Soaking the HSY molecular sieve in a mixed salt solution at 55 ℃ until water is fully evaporated, and roasting at 500 ℃ for 1.5 hours to obtain a modified molecular sieve B, wherein the total load of La, pr and Co in the modified molecular sieve B is 0.5% of the total load of the HSY molecular sieve.
2. Preparation of modified kaolin:
1. modified kaolin a:
(1) Repeatedly pumping and filtering kaolin with deionized water for 3 times, drying at 350 ℃ for 1.5 hours, adding 3% phosphoric acid solution, respectively stirring at 0 ℃, 15 ℃ and 35 ℃ for 20 minutes, filtering, washing with deionized water, and filtering for 4 times to obtain pretreated kaolin;
(2) Presintering the pretreated kaolin at 300 ℃ for 1.5 hours, and then adjusting the temperature to 750 ℃ for calcining for 1.5 hours to obtain the modified kaolin A.
2. Modified kaolin B:
(1) Repeatedly pumping and filtering kaolin with deionized water for 3 times, drying at 350 ℃ for 1.5 hours, adding 3% phosphoric acid solution, stirring at normal temperature for 60 minutes, filtering, washing with deionized water, and filtering for 4 times to obtain pretreated kaolin;
(2) Presintering the pretreated kaolin at 300 ℃ for 1.5 hours, and then adjusting the temperature to 750 ℃ for calcining for 1.5 hours to obtain the modified kaolin B.
Example 2:
preparation of heavy metal resistant catalytic cracking auxiliary agent:
(1) Preparing materials: preparing a molecular sieve, kaolin and aluminum sol according to a mass ratio of 28:48:19;
(2) Mixing molecular sieve and kaolin, adding deionized water to prepare primary slurry, and controlling the solid content of the primary slurry to be 50%;
(3) Treating the primary slurry by adopting liquid nitrogen for 8min, taking out the frozen primary slurry, crushing and sieving the crushed primary slurry by a 30-mesh sieve to obtain a pretreated material for later use;
(4) Adding deionized water into the pretreated material mixed aluminum sol, stirring to prepare secondary slurry with the solid content of 35%, pulping, and spray-drying to prepare microspheres for later use;
(5) And (3) roasting the microspheres for 50min at 400 ℃, 700 ℃ and 900 ℃ in sequence, and then sieving the roasted microspheres with a 20-mesh sieve to obtain the heavy metal resistant catalytic cracking auxiliary agent.
According to the preparation method, the heavy metal resistant catalytic cracking auxiliary agents of each group are prepared according to the molecular sieve and kaolin selection of the following table 2:
TABLE 2
Comparative example 1:
preparation of heavy metal resistant catalytic cracking auxiliary agent:
(1) Preparing materials: preparing a modified molecular sieve A, modified kaolin A and aluminum sol according to a mass ratio of 28:48:19;
(2) Adding deionized water into the mixed alumina sol of the modified molecular sieve A and the modified kaolin A, stirring to prepare slurry with the solid content of 35%, pulping, and spray-drying to prepare microspheres for later use;
(3) And (3) roasting the microspheres at 400 ℃, 700 ℃ and 900 ℃ for 50min, taking out, and sieving with a 20-mesh sieve to obtain the heavy metal resistant catalytic cracking additive.
Comparative example 2:
preparation of heavy metal resistant catalytic cracking auxiliary agent:
(1) Preparing materials: preparing a molecular sieve, kaolin and aluminum sol according to a mass ratio of 28:48:19;
(2) Mixing molecular sieve and kaolin, adding deionized water to prepare primary slurry, and controlling the solid content of the primary slurry to be 50%;
(3) Treating the primary slurry by adopting liquid nitrogen for 8min, taking out the frozen primary slurry, crushing and sieving the crushed primary slurry by a 30-mesh sieve to obtain a pretreated material for later use;
(4) Adding deionized water into the pretreated material mixed aluminum sol, stirring to prepare secondary slurry with the solid content of 35%, pulping, and spray-drying to prepare microspheres for later use;
(5) And roasting the microspheres at 900 ℃ for 1.5 hours, and then sieving the roasted microspheres with a 20-mesh sieve to obtain the heavy metal resistant catalytic cracking additive.
Comparative example 3:
preparation of heavy metal resistant catalytic cracking auxiliary agent:
(1) Preparing materials: preparing a molecular sieve, kaolin and aluminum sol according to a mass ratio of 28:48:19;
(2) Adding molecular sieve and kaolin mixed aluminum sol into deionized water, stirring to prepare secondary slurry with the solid content of 35%, pulping, and spray-drying to prepare microspheres for later use;
(3) And (3) roasting the microspheres at 400 ℃, 700 ℃ and 900 ℃ for 50min, taking out, and sieving with a 20-mesh sieve to obtain the heavy metal resistant catalytic cracking additive.
And (3) detection:
daqing oilfield raw oil is selected as an experimental material, and the performance of the raw oil is shown in the following table 3:
TABLE 3 Table 3
The catalytic performances of the heavy metal resistant catalytic cracking auxiliary agents prepared in the experimental groups 1-5 and the heavy metal resistant catalytic cracking auxiliary agents prepared in the comparative examples 1-3 in the above example 2 were respectively detected by adopting an XGL-2X 3 type fixed fluidized bed (reaction at 500 ℃), each group of the heavy metal resistant catalytic cracking auxiliary agents was put into a quartz tube before the experiment, the quartz tube was heated to 750 ℃ in an aging furnace, deionized water was introduced into the quartz tube, the introduced flow rate was 24 mL/h, the hydrothermal reaction aging was carried out for 16h, the temperature was taken out and dried to constant weight, and the specific experimental results are shown in the following table 4:
TABLE 4 Table 4
According to the table above: the experimental group 1 is compared with the experimental group 4, wherein the heavy oil conversion rate of the experimental group 1 is 94.75%, and the heavy oil conversion rate of the experimental group 4 is 91.24%, which is different by more than 3%, namely, the heavy metal resistant catalytic cracking auxiliary agent prepared by adding the modified molecular sieve prepared by adopting the step-by-step impregnation method in the experimental group 1 has higher heavy oil conversion rate compared with the heavy metal resistant catalytic cracking auxiliary agent prepared by adding the modified molecular sieve prepared by adopting the one-step impregnation method in the experimental group 4; the comparison of the experimental group 1 and the experimental group 2 shows that the catalyst prepared by adding the kaolin modified at the temperature of 0 ℃ and the temperature of 15 ℃ and the temperature of 35 ℃ in the experimental group 1 has higher heavy oil conversion rate.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The heavy metal resistant catalytic cracking auxiliary agent is characterized by comprising 25-30 of modified molecular sieve, 42-50 of modified kaolin and 17-20 of alumina sol in mass ratio, wherein the modified molecular sieve is obtained by loading La, pr and Co with equal mass by adopting an HSY molecular sieve, and the total loading amount of La, pr and Co is 0.2-1.2% of the total loading amount of the HSY molecular sieve;
the specific preparation method of the modified molecular sieve comprises the following steps:
s1-1, preparing a metal salt solution of La, pr and Co;
s1-2, stirring an HSY molecular sieve with deionized water for 20-30min under the environment of the pressure of 2-4Mpa and the temperature of 50-80 ℃, repeatedly carrying out suction filtration for 2-3 times, and then drying to obtain a pretreated HSY molecular sieve;
S1-3, sequentially soaking the pretreated HSY molecular sieve in each metal salt solution, roasting at 480-550 ℃ for 20-40min after single soaking and drying, roasting at 480-550 ℃ for 1-2h after final soaking and drying, and grinding and sieving with a 20-mesh sieve to obtain a modified molecular sieve;
The modified kaolin is prepared by washing kaolin with water, modifying with phosphoric acid, presintering and calcining, and the specific preparation method comprises the following steps:
s2-1, repeatedly carrying out suction filtration on kaolin by deionized water for 2-4 times, drying, adding 3% phosphoric acid solution, respectively stirring at the temperature of 0 ℃, 15 ℃ and 35 ℃ for 15-30min, filtering, and washing and filtering by deionized water for 4-5 times to obtain pretreated kaolin;
S2-2, presintering the pretreated kaolin at the temperature of 280-350 ℃ for 1-2 hours, and then adjusting the temperature to 600-800 ℃ for calcining for 1-2 hours to obtain the modified kaolin.
2. The heavy metal resistant catalytic cracking aid according to claim 1, wherein: the preparation method of the metal salt solution of La, pr and Co in the step S1-1 is to dissolve LaCl 3、Pr(NO3)3、CoCl2 into deionized water respectively.
3. The heavy metal resistant catalytic cracking aid according to claim 1, wherein: the pretreatment of the HSY molecular sieve in the step S1-3 is sequentially carried out by immersing the pretreated HSY molecular sieve in a metal salt solution with the temperature of 50-60 ℃ and transferring the HSY molecular sieve into an oven with the temperature of 70-80 ℃ for drying to constant weight after the surface is preliminarily dried.
4. The heavy metal resistant catalytic cracking aid according to claim 1, wherein: the drying mode in the step S2-1 is drying at the temperature of 350 ℃ for 1-2h.
5. A process for the preparation of an anti-heavy metal catalytic cracking aid according to any one of claims 1 to 4, comprising the steps of:
(1) Mixing a modified molecular sieve and modified kaolin, and adding deionized water to prepare a primary slurry;
(2) Treating the primary slurry by adopting liquid nitrogen for 5-10min, taking out the frozen primary slurry, crushing the primary slurry, and sieving the crushed primary slurry by a 20-40-mesh sieve to obtain a pretreated material for later use;
(3) Adding deionized water into the pretreated material mixed aluminum sol, stirring to prepare secondary slurry, pulping, and spray-drying to prepare microspheres for later use;
(4) The microspheres are respectively baked for 30-80min at 300-500 ℃, 600-800 ℃ and 850-900 ℃ and then are sieved by a 20-mesh sieve, thus obtaining the heavy metal resistant catalytic cracking auxiliary agent.
6. The method for preparing heavy metal resistant catalytic cracking aid according to claim 5, wherein the solid content of the preliminary slurry in the step (1) is 45-65%.
7. The method for preparing heavy metal resistant catalytic cracking aid according to claim 5, wherein the solid content of the secondary slurry in the step (3) is 25-45%.
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