CN116212940B - Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity - Google Patents
Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity Download PDFInfo
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- CN116212940B CN116212940B CN202310204732.1A CN202310204732A CN116212940B CN 116212940 B CN116212940 B CN 116212940B CN 202310204732 A CN202310204732 A CN 202310204732A CN 116212940 B CN116212940 B CN 116212940B
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- dry basis
- catalytic cracking
- cracking catalyst
- roasting
- chloride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 239000000571 coke Substances 0.000 title claims abstract description 16
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 18
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 18
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052621 halloysite Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- -1 rare earth chloride Chemical class 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000009738 saturating Methods 0.000 claims description 5
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- 239000011670 zinc gluconate Substances 0.000 claims description 2
- 235000011478 zinc gluconate Nutrition 0.000 claims description 2
- 229960000306 zinc gluconate Drugs 0.000 claims description 2
- 229940071566 zinc glycinate Drugs 0.000 claims description 2
- UOXSXMSTSYWNMH-UHFFFAOYSA-L zinc;2-aminoacetate Chemical compound [Zn+2].NCC([O-])=O.NCC([O-])=O UOXSXMSTSYWNMH-UHFFFAOYSA-L 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 238000002161 passivation Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C10G11/08—Halides
-
- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a preparation method of a catalytic cracking catalyst with excellent coke and dry gas selectivity, which comprises the steps of roasting, modifying and reaming kaolin, and adding metal passivation active ingredients at a proper position by adopting a proper method, so that the prepared catalyst has proper pore diameter, pore distribution and acid quantity, can effectively reduce the toxic action of harmful metals, and has obvious coke and dry gas selectivity advantages.
Description
Technical Field
The invention relates to a preparation method of a catalytic cracking catalyst with excellent coke and dry gas selectivity, belonging to the field of catalyst preparation.
Background
Before 2030, the national promise is that the burning activities of fossil energy sources such as coal, petroleum, natural gas and the like, industrial production processes, land utilization changes, forestry and other activities and the greenhouse gas emission (also including the greenhouse gas emission caused by the use of outsourced electric power, heating power and the like) are not increased, and peak values are reached.
How should the refinery industry deal with? The general idea is to reduce the energy consumption of processing ton oil of oil refining, wherein the advanced oil refining energy consumption is lower than 50 kg standard oil/ton crude oil, and the domestic standard oil/ton crude oil is 60-70 kg; changing the fuel structure of the refinery, after all, 33% of the refinery carbon emissions are fuel combustion from the refinery; as many refineries as possible find a balance between complexity and number of devices, the more complex refineries, the higher the carbon emissions. A simple refinery, 0.2 ton of carbon/ton of crude oil, a complex refinery, up to 0.4 ton of carbon/ton of crude oil. A small refinery, which is to be transformed or the productivity is to be combined; large refineries, fuel construction must be changed; the oil refining process must be simple and highly operable, striving for simple processes, yielding complex products. Oil refining is transformed into low processing energy consumption, large device scale, clean fuel structure (even electric heating process medium), relatively simple process and chemical type.
Catalytic cracking units are one of the primary sources of CO 2 emissions from refineries. From the viewpoints of reducing CO2 emission of a catalytic cracking device and improving device benefits, the most economical, convenient and effective method for reducing carbon emission of catalytic cracking is to develop a novel catalytic cracking catalyst or catalytic auxiliary agent aiming at reducing coke yield, and is mainly realized by an ultra-stable Y-type molecular sieve technology and preparing a catalyst carrier material with good pore structure and acid distribution.
Molecular sieve technology for reducing coke yield is mainly focused on the preparation research of ultrastable Y-type molecular sieves, such as CN200810102243.0, CN101537366A and the like. In the aspect of carriers, the diffusion efficiency of reactants and products needs to be improved, the overcracking is reduced, meanwhile, the acidity type is modulated, and the reaction selectivity of an acid center is improved-the synthesis of a material with high pore volume, large pore diameter and high B/L acid ratio is a main research direction.
CN03147975.8 discloses a mesoporous silica-alumina material having a phase structure of pseudo-boehmite, and the anhydrous chemical expression by weight of oxide is: (0-0.3) Na2O (40-90) Al2O3 (10-60) SiO2, the specific surface area is 200-400 m2/g, the pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, and the most probable pore diameter is 5-15 nm.
CN201110251792.6 discloses an acidic silica-alumina catalytic material having a pseudo-boehmite crystalline phase structure; the anhydrous chemical expression of the catalyst is as follows, based on the weight of oxide: (0-0.2) Na2O (44-46) SiO2 (54-56) Al2O3, the pore volume is 0.5-1.0 ml/g, the average pore diameter is 8-15 nm, and the ratio of pyridine infrared B acid to L acid measured at 200 ℃ of the catalytic material is 0.130-0.150.
CN201110251761.0 discloses a mesoporous acidic silicon aluminum catalytic material, which has a pseudo-boehmite crystalline phase structure, the pore volume is 1.0-2.0 ml/g, the average pore diameter is 8-20 nm, and the ratio of pyridine infrared B acid to L acid measured at 200 ℃ of the catalytic material is 0.060-0.085.
CN201210409663.X discloses a preparation method of silicon-containing aluminum oxide dry glue, the prepared silicon-containing aluminum oxide dry glue is roasted for 2-6 hours at 500-950 ℃, and the properties of the obtained silicon-containing aluminum oxide are as follows: the pore volume is 0.55-1.10 ml/g, and the pore distribution is as follows: the pore volume of the pores with the pore diameter of 10 nm-50 nm accounts for 30-80% of the total pore volume, and the acid/L acid of B is 0.110-0.251.
Zheng Jinyu and the like successfully prepare the disordered mesoporous silica alumina material (JSA) with pseudo-boehmite structure through the processes of gelatinization, aging and the like, wherein the disordered mesoporous silica alumina material has higher specific surface area and pore volume, the specific surface area is more than 300m < 2 >/g, the pore volume is more than 0.7cm < 3 >/g, the pore diameter can be between 6 and 7nm, and the disordered mesoporous silica alumina material contains L acid centers and B acid centers, but the L acid quantity is obviously higher than that of the B acid centers.
The existing defects are that: (1) The diffusion advantage of the mesoporous matrix is amplified, and the excessive cracking is not considered as long as the diffusion is fast, or the acidity and the acid quantity of the matrix are considered, and the influence of metal poisoning on the selectivity of coke and dry gas is seldom considered; (2) The self-made mesoporous matrix is not easy to acidify and bond, more binders are needed or the aluminum colloid forming ratio is improved to ensure the abrasion performance, too much binders can block the pore channels of the molecular sieve, too much aluminum colloid is added to the too high aluminum colloid forming ratio to introduce a large amount of chloride ions, and when the catalyst is roasted or added into an FCC device, the chloride ion release treatment is serious to the corrosion of equipment.
Disclosure of Invention
In order to solve the defects of the technology, the invention provides a preparation method of a catalytic cracking catalyst with excellent coke and dry gas selectivity, which comprises the following specific steps:
(1) Adding a certain proportion of magnesium chloride and rare earth chloride when the kaolin is pulped, and uniformly stirring;
(2) Drying the slurry, saturating and impregnating with organic zinc, and roasting;
(3) Adding water into the roasting material, pulping, adding a certain proportion of halloysite, adding a compound acid, reacting for a period of time, and continuously adding a certain proportion of pseudo-boehmite, wherein the whole process needs measures to control the temperature rise;
(4) Adding REUSY molecular sieve and aluminum sol in a certain proportion into the slurry, and carrying out spray granulation;
(5) When the sprayed particles enter a roasting furnace, introducing antimony chloride by a gas phase method, fully contacting the antimony chloride with the particles, and filtering, washing and drying after roasting to obtain the target.
The adding amount of magnesium chloride in the step (1) is (0.3-0.8) wt% of kaolin dry basis calculated by Mg0, and the adding amount of rare earth chloride is (0.5-1.2) wt% of kaolin dry basis calculated by RE 2O3;
the addition amount of the organic zinc in the step (2) is (0.6-0.9) wt% of the kaolin dry basis calculated by ZnO, and can be zinc gluconate, zinc citrate or zinc glycinate;
the addition amount of the compound acid in the step (3) is (8-15) wt% of the dry basis of the halloysite, and the addition amount of the pseudo-boehmite is (5-12) wt% of the dry basis of the halloysite calculated by Al 2O3;
The REUSY molecular sieve in the step (4) is added in an amount of (30-43) wt% based on the dry basis of the title, and the aluminum sol is added in an amount of (2-6) wt% based on the dry basis of the title in terms of Al 2O3;
in the step (5), the adding amount of the antimony chloride is (0.08-0.25) weight percent of the dry basis of the title compound, the antimony chloride is heated to 230 ℃ firstly, and the antimony chloride enters the furnace end of the roasting furnace to be fully contacted with catalyst particles below the spraying tower through a nozzle in a gaseous state.
The dry basis ratio of the kaolin to the halloysite is (0.6-2.5): 1.
The invention has the advantages that:
(1) After the kaolin is baked into partial soil, the composite acid is used for modification, so that a proper reaming effect can be generated, the multi-water kaolin is treated by the composite acid, the tubular lamellar structure of the multi-water kaolin is stretched, and a part of activated alumina can form substances with bonding performance with the composite acid, so that the addition proportion of an externally added chlorine-containing binder is reduced;
(2) The alkaline earth metal, rare earth oxide, zinc, antimony and other elements in a certain proportion are added, so that metals such as vanadium, nickel, iron and the like can be passivated, and the metals can cause the increase of coke and dry gas yield;
(3) The organic zinc which can be used for food addition is soluble, so that the poison of other zinc types to workers and the environment during preparation is avoided, and the zinc is finally mainly loaded on the particle surface due to the fact that toxic metals are basically deposited on the particle surface by adopting the saturated impregnation of the organic zinc.
(4) The antimony chloride is gasified above 223.5 ℃, the contact of the antimony with larger toxicity with people is avoided by adopting a gas phase precipitation method, the antimony is contacted with low-temperature catalyst particles falling from the bottom of the spraying tower, the antimony is adsorbed on the surfaces of the particles after being liquefied, and then the antimony is decomposed and fixed on the surfaces of the catalyst particles.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.
The raw materials used in the examples were as follows:
The following materials were all taken from the manufacturing plant of Qingdao Huicheng environmental protection technology group Co., ltd.
Kaolin: 75wt% on a dry basis;
magnesium chloride solution: 5wt%, calculated as MgO;
rare earth chloride solution: 20.3wt%, calculated as RE 2O3
Organozinc solution: 3.2 to 4.2wt%, calculated as ZnO;
Halloysite: 63.5wt% on a dry basis;
Complex acid: concentration is 35%;
pseudo-boehmite: 65wt% on a dry basis;
REUSY molecular sieve: 15wt% of burning;
aluminum sol: 21.2%, calculated as Al 2O3;
Example 1:
(1) 1333g of kaolin is added with water for pulping, 80g of magnesium chloride and 54.2g of rare earth chloride are added, and the mixture is stirred uniformly;
(2) Drying the slurry, saturating and impregnating 200g (3.25%) of organic zinc, and roasting;
(3) Adding water into the roasting material, pulping, adding 1575g of multi-water kaolin, adding 314g of complex acid, reacting for a period of time, and continuously adding 590g of pseudo-boehmite, wherein measures are needed to control the temperature rise in the whole process;
(4) Adding 1906gREUSY molecular sieve and 603g aluminum sol into the slurry, and granulating by spraying;
(5) When the sprayed particles enter a roasting furnace, 6.43g of antimony chloride is introduced by a gas phase method and fully contacted with the particles, and the particles are filtered, washed and dried after roasting, and then the CAT-1 is marked.
Example 2:
(1) 1333g of kaolin is added with water for pulping, 120g of magnesium chloride and 39.4g of rare earth chloride are added, and the mixture is stirred uniformly;
(2) Drying the slurry, saturating and impregnating 200g (3.75%) of organic zinc, and roasting;
(3) Adding water into the roasting material, pulping, adding 2362g of halloysite, adding 600g of complex acid, reacting for a period of time, and continuously adding 448g of pseudo-boehmite, wherein measures are needed to control the temperature rise in the whole process;
(4) Adding 2168gREUSY molecular sieve and 915g aluminum sol into the slurry, and spraying and granulating;
(5) When the sprayed particles enter a roasting furnace, 13.7g of antimony chloride is introduced by a gas phase method and fully contacted with the particles, and the particles are filtered, washed and dried after roasting, and then the CAT-2 is marked.
Example 3:
(1) 1333g of kaolin is added with water for pulping, 160g of magnesium chloride and 29.6g of rare earth chloride are added, and the mixture is stirred uniformly;
(2) Drying the slurry, saturating and impregnating 200g (4.25%) of organic zinc, and roasting;
(3) Adding water into the roasting material, pulping, adding 787g of halloysite, adding 114g of composite acid, reacting for a period of time, and continuously adding 656g of pseudo-boehmite, wherein measures are needed to control the temperature rise in the whole process;
(4) Adding 1588gREUSY molecular sieve 1005g aluminum sol into the slurry, and granulating by spraying;
(5) When the sprayed particles enter a roasting furnace, 16.8g of antimony chloride is introduced by a gas phase method and fully contacted with the particles, and the particles are filtered, washed and dried after roasting, and then the CAT-3 is marked.
The catalyst is impregnated with metals such as iron, nickel, vanadium and the like in a cyclic pollution mode, the contrast agent is a formula for preparing the same molecular sieve content and activity conventionally, proper hydrothermal aging treatment is carried out, and an ACE-AP evaluation device is used for comparison evaluation. The data of the raw oil used are shown in Table 1, and the evaluation data are shown in Table 2 and Table 3.
TABLE 1 oil Properties of raw materials
Table 2 evaluation data after iron impregnation
Table 3 comparative evaluation data after Nickel and vanadium impregnation
As can be seen from the comparison and evaluation data, the catalyst provided by the invention has the advantages that the selectivity of dry gas and coke is obviously improved under the condition of higher metal content, and the corresponding light recovery and liquid recovery are also obviously improved, so that the performance is excellent.
Claims (2)
1. A method for preparing a catalytic cracking catalyst with excellent coke and dry gas selectivity, which comprises the following steps:
(1) Adding a certain proportion of magnesium chloride and rare earth chloride when the kaolin is pulped, wherein the adding amount of the magnesium chloride is (0.3-0.8) wt% of the kaolin dry basis based on MgO, and the adding amount of the rare earth chloride is (0.5-1.2) wt% of the kaolin dry basis based on RE 2O3, and uniformly stirring;
(2) Drying the slurry, saturating and impregnating with organic zinc, wherein the addition amount of the organic zinc is (0.6-0.9) wt% of the kaolin dry basis based on ZnO, and roasting;
(3) Adding water into the roasting material, pulping, and adding a certain proportion of halloysite, wherein the proportion of the halloysite to the dry basis of the halloysite is 1: (0.6-2.5), adding a compound acid, wherein the addition amount of the compound acid is (8-15) wt% of the dry basis of the halloysite, reacting for a period of time, continuously adding a certain proportion of pseudo-boehmite, and taking Al 2O3 as (5-12) wt% of the dry basis of the halloysite, wherein the whole process needs measures to control the temperature rise;
(4) Adding REUSY molecular sieve and aluminum sol in a certain proportion into the slurry, wherein the adding amount of REUSY molecular sieve is (30-43) wt% of the total dry basis of the catalytic cracking catalyst with excellent coke and dry gas selectivity, and the adding amount of aluminum sol is (2-6) wt% of the total dry basis of the catalytic cracking catalyst with excellent coke and dry gas selectivity calculated by Al 2O3, and carrying out spray granulation;
(5) When the sprayed particles enter a roasting furnace, introducing antimony chloride by a gas phase method, wherein the adding amount of the antimony chloride is (0.08-0.25) weight percent of the total dry basis of the catalytic cracking catalyst with excellent coke and dry gas selectivity, heating the antimony chloride to 230 ℃, enabling the antimony chloride to enter a furnace end of the roasting furnace through a nozzle in a gas state mode to fully contact with catalyst particles arranged below a spraying tower, and filtering, washing and drying after roasting is finished, so that the catalytic cracking catalyst with excellent coke and dry gas selectivity is obtained.
2. The process according to claim 1, wherein in step (2), the organozinc is selected from zinc gluconate, zinc citrate and zinc glycinate.
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