CN115025806A - Preparation method of iron pollution resistant catalytic cracking catalyst - Google Patents
Preparation method of iron pollution resistant catalytic cracking catalyst Download PDFInfo
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- CN115025806A CN115025806A CN202210543570.XA CN202210543570A CN115025806A CN 115025806 A CN115025806 A CN 115025806A CN 202210543570 A CN202210543570 A CN 202210543570A CN 115025806 A CN115025806 A CN 115025806A
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- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 9
- 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 27
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 19
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 14
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 12
- 229940007718 zinc hydroxide Drugs 0.000 claims description 12
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 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 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000020477 pH reduction Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 7
- 239000010779 crude oil Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract 2
- 230000004048 modification Effects 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052622 kaolinite Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 210000004911 serous fluid Anatomy 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- -1 rare earth compound Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 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
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an iron pollution resistant catalytic cracking catalyst. The method is to improve the specific surface area and pore volume of the matrix of the catalyst by pore-enlarging modification of kaolin, and simultaneously improve the iron pollution resistance of the catalyst by aluminum-rich and zinc-rich modification on the surface of catalyst particles. The catalyst shows better iron pollution resistance and excellent product selectivity under higher iron loading, thereby providing a convenient and feasible solution for processing crude oil with high iron content.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of an iron pollution resistant catalytic cracking catalyst.
Background
At present, catalytic cracking plays a very important role in the field of petroleum refining as a main means of crude oil secondary processing, and the performance of a catalytic cracking catalyst is a key factor which directly influences product distribution. With the increasing weight and deterioration of crude oil, the metal content in the raw material is increased, and the main metal elements include vanadium and nickel, as well as iron, calcium, sodium, copper and the like. Therefore, higher demands are made on the metal contamination resistance of the catalyst. At present, the research on the resistance to nickel-vanadium pollution is more, but less iron is needed, and two reasonable explanations are summarized for the poisoning mechanism of iron, wherein the first explanation is as follows: iron is similar to other metals such as nickel, vanadium and the like, the iron mainly exists in macromolecular hydrocarbon of the raw material, iron is continuously deposited on the outer surface of particles in the process of carrying out pre-cracking reaction on the macromolecular components of the raw material on a substrate, and is gradually enriched on the outer surface of the particles due to weaker migration activity, so that the pore passages of the substrate are blocked, the accessibility of an active center is reduced, the heavy oil conversion capacity of the catalyst is reduced, and the yield of a target product is poor; the second explanation: the pore channel of the matrix is blocked not only because of the physical deposition of iron, but also because iron can form low-melting-point eutectic with silicon, calcium, sodium and the like in the matrix, the surface of catalyst particles can be in a glass shape in the melting process, a nodular bulge is formed when the temperature is reduced, and a compact shell layer with the diameter of 1-3 mu m is formed on the surface, so that the internal diffusion mass transfer of oil gas molecules is influenced, the number of active centers is greatly reduced, and the fluidization of the catalyst in the device is influenced in severe cases.
Based on the above destruction mechanism, aiming at improving the iron pollution resistance, on one hand, the specific surface area and the pore volume of the catalyst substrate component are increased, the eutectic with low melting point is dispersed, and the blockage of the eutectic to the catalyst pore channel is reduced; on the other hand, the content of the alumina in the catalyst substrate is increased, so that the iron oxide is deposited on the surface of the alumina as much as possible to reduce the generation of low-melting eutectic substances.
At present, the patent technology related to the preparation of the catalyst for resisting iron pollution is few, so that a feasible catalyst preparation process technology is urgently needed, and a feasible catalyst use scheme is provided for processing high-iron crude oil.
CN107303507A discloses a method for preparing alumina containing phosphorus and silicon, the alumina carrier prepared by the method keeps the characteristics of high specific surface area and large pore volume of pseudo-boehmite, and the acid content of the alumina carrier can be simply adjusted within a larger range by using the contents of phosphorus and silicon, so that the carrier can be used in a plurality of fields.
CN102188963A discloses a method for modifying kaolin, which comprises using kaolin as a raw material, first roasting the kaolin at a high temperature, then uniformly stirring the high-temperature roasted kaolin with an additional aluminum source and an acid solution to obtain a mixed slurry, and reacting under certain conditions, and then directly using the mixed slurry as a raw material for preparing a catalytic cracking catalyst without filtering. The modified kaolin has developed medium-large pore volume and certain activity, and the slurry containing the modified kaolin also has certain binding property, so that the catalyst prepared by the slurry containing the modified kaolin has stronger heavy metal resistance.
CN109692694A discloses a macroporous kaolinite, its preparation and application, the macroporous kaolinite contains rare earth, the average pore diameter is 2-50nm, the pore volume of the pore with pore diameter of 10-50nm accounts for more than 80% of the total pore volume. The preparation method of the macroporous kaolinite comprises the following steps: the preparation method comprises the following steps of carrying out first roasting on kaolin, forming a mixture of the kaolin subjected to the first roasting, a first acidic solution and an optional rare earth compound, carrying out first treatment, then carrying out second roasting, mixing the mixture with a second acidic solution, a pore-expanding agent and the optional rare earth compound, carrying out second treatment, filtering and drying to obtain the macroporous kaolinite, wherein the rare earth compound is introduced in at least one of the first treatment and the second treatment. The macroporous kaolinite has high cracking activity, is used for a catalyst cracking catalyst to replace clay, and has the advantages of good coke selectivity, strong heavy metal pollution resistance and high gasoline yield on the premise of equivalent rare earth content.
The invention content is as follows:
the invention discloses a preparation method of an anti-iron pollution catalytic cracking catalyst, aiming at improving the anti-iron pollution capacity of the catalyst and realizing the purpose of stably and efficiently processing high-iron crude oil, and the method comprises the following specific steps:
(1) mixing kaolin and phosphorus-aluminum glue, pulping, controlling the solid content to be more than or equal to 50%, and stirring for more than or equal to 6 hours;
(2) adding polyethylene glycol into the aluminum sol, and stirring for later use;
(3) adding water into pseudo-boehmite for pulping, and adding boric acid for pre-acidification;
(4) adding water into REY molecular sieve, pulping, and stirring for later use;
(5) and (3) mixing the serosity in the steps (1), (2), (3) and (4) in a parallel flow manner, adding hydrochloric acid, controlling the pH value to be 2.2-3.0, and performing spray granulation, roasting, washing and drying to obtain a finished product.
In the step (1), adding P as the proportion of the phosphor-aluminum glue 2 O 5 Accounting for 5-10 wt% of the dry basis of the finished product.
In the step (1), the composition of the phosphor-aluminum paste is P 2 O 5 With Al 2 O 3 The molar ratio is 4.5-10.
In the step (2), the molecular weight of the polyethylene glycol is 1000-2000g/mol, and the adding proportion accounts for Al 2 O 3 0.001-0.01 wt% of the aluminum solution.
In the step (3), the boric acid is added in the proportion of H 3 BO 3 Calculated as Al 2 O 3 0.1-0.3 wt% of pseudoboehmite.
In the step (5), an opening is added on a pipeline connected with the roasting furnace at the bottom of the spraying tower so as to realize the purpose of continuously adding zinc hydroxide, wherein the adding proportion of the zinc hydroxide is 0.1-0.5 wt% of the dry basis of the finished product calculated by ZnO. The innovation points or advantages of the invention are as follows:
(1) firstly, the kaolin is pulped with the phosphor-aluminum glue, and the composition of the phosphor-aluminum glue is P 2 O 5 With Al 2 O 3 The molar ratio is 4.5-10, except for being used as a binder, the pH value of the slurry is lower due to excessive phosphoric acid, the temperature of the slurry is raised by controlling the pulping solid content and the stirring time and the shearing friction of stirring, the two act together to dissolve a small part of alumina of the kaolin into the slurry, pore channels are dredged and widened, and the height is increasedThe specific surface area of ridge soil can effectively reduce the hole plugging effect of iron pollution.
(2) Polyethylene glycol is added into the aluminum sol, so that the dispersion and surface tension of micelles are improved, the slurry is quickly shrunk into a spherical shape in the spray drying process, and the aluminum sol is more dispersed on the outer surface of the particles, so that the aim of enriching aluminum on the surface is fulfilled.
(3) The boric acid pre-acidified pseudo-boehmite can form holes in a certain proportion by utilizing the characteristics of 169 ℃ of melting point (decomposition) and 300 ℃ of boiling point of boric acid during roasting, thereby improving the diffusion performance of the catalyst.
(4) The zinc hydroxide and the catalyst particles enter a roasting furnace together, the zinc hydroxide is decomposed into zinc oxide and water at 125 ℃, the zinc oxide is adsorbed on the surfaces of the catalyst particles, and the zinc oxide and iron can form high-melting-point substances to achieve the purpose of iron fixation, so that the toxicity of the iron is reduced.
(5) The excessive phosphoric acid in the phosphorus-aluminum gel contacts with various substances to form phosphorus hydroxyl, so that the acid center number of the catalyst is increased, and the cracking capability of the catalyst is improved.
Compared with the catalyst prepared by the conventional method, the catalyst prepared by the technical means has higher mesopore and macropore specific surface area and more mesopore and strong acid center quantity, has excellent iron pollution resistance in application, and can reduce the generation of low value-added products such as dry gas, coke and the like, thereby improving the economic benefit of oil refining.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples, which are intended to illustrate only some of the embodiments of the present invention and are not intended to limit the scope of the present invention.
The specification of the raw materials used in the embodiment of the invention is as follows:
kaolin: technical grade, china kaolin ltd, 25.5% scorch;
aluminum sol: self-produced Al 2 O 3 The content was 21.5 wt%;
polyethylene glycol: analytically pure, molecular weight 1000-;
pseudo-boehmite: industrial grade, Shandong division of aluminum, Inc., Shandong province, China, 29.5 wt% burned;
REY molecular sieve: self-production, RE 2 O 3 The content is 7.5-9.0 wt%, and the scorch weight is 25.0 wt%;
phosphorus-aluminum glue: self-made, P 2 O 5 +Al 2 O 3 The content is 40 wt%;
hydrochloric acid: analyzing and purifying;
zinc hydroxide: and (5) analyzing and purifying.
Example 1
(1) Weighing 700 g of kaolin and 160 g of phosphorus-aluminum adhesive (the phosphorus-aluminum ratio is 4.5), adding 600 g of water, controlling the solid content of the slurry to be more than or equal to 50%, mixing and pulping for 16 hours, and controlling the temperature of the slurry to be between 80 and 90 ℃;
(2) weighing 200 g of alumina sol and 0.007 g of polyethylene glycol, adding the polyethylene glycol into the alumina sol, and uniformly stirring for later use;
(3) weighing 360 g of pseudo-boehmite, adding 350 g of water, pulping, and adding 0.5 g of boric acid;
(4)600 g of REY molecular sieve is added with 600 g of water and pulped for standby;
(5) and (3) adding the serous fluid of (1), (2), (3) and (4) into the mixture in a cocurrent flow manner, mixing and pulping, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, performing spray drying, adding 3 g of zinc hydroxide during roasting, washing and drying, and marking a sample as Cat-1.
Example 2
(1) Weighing 700 g of kaolin and 200 g of phosphorus-aluminum adhesive (the phosphorus-aluminum ratio is 4.5), adding 550 g of water, controlling the solid content of the slurry to be more than or equal to 50%, mixing and pulping for 16 hours, and controlling the temperature of the slurry to be between 80 and 90 ℃;
(2) weighing 200 g of alumina sol and 0.007 g of polyethylene glycol, adding the polyethylene glycol into the alumina sol, and uniformly stirring for later use;
(3) weighing 360 g of pseudo-boehmite, adding 350 g of water, pulping, and adding 0.5 g of boric acid;
(4)600 g of REY molecular sieve is added with 600 g of water and pulped for standby;
(5) and (3) adding the serous fluid of (1), (2), (3) and (4) into the mixture in a cocurrent flow manner, mixing and pulping, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, performing spray drying, adding 3 g of zinc hydroxide during roasting, washing and drying, and marking a sample as Cat-2.
Example 3
(1) Weighing 700 g of kaolin and 250 g of phosphorus-aluminum adhesive (the phosphorus-aluminum ratio is 4.5), adding 500 g of water, controlling the solid content of the slurry to be more than or equal to 50%, mixing and pulping for 16 hours, and controlling the temperature of the slurry to be between 80 and 90 ℃;
(2) weighing 200 g of alumina sol and 0.007 g of polyethylene glycol, adding the polyethylene glycol into the alumina sol, and uniformly stirring for later use;
(3) weighing 360 g of pseudo-boehmite, adding 350 g of water, pulping, and adding 0.5 g of boric acid;
(4)600 grams of REY molecular sieve is added with 600 grams of water and beaten for standby;
(5) and (3) adding the serous fluid of (1), (2), (3) and (4) into the mixture in a cocurrent flow manner, mixing and pulping, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, performing spray drying, adding 5 g of zinc hydroxide during roasting, washing and drying, and marking a sample as Cat-3.
Example 4
(1) Weighing 700 g of kaolin and 160 g of phosphorus-aluminum adhesive (the phosphorus-aluminum ratio is 6.0), adding 500 g of water, controlling the solid content of the slurry to be more than or equal to 50%, mixing and pulping for 16 hours, and controlling the temperature of the slurry to be between 80 and 90 ℃;
(2) weighing 200 g of aluminum sol and 0.007 g of polyethylene glycol, adding the polyethylene glycol into the aluminum sol, and uniformly stirring for later use;
(3) weighing 360 g of pseudo-boehmite, adding 350 g of water, pulping, and adding 0.8 g of boric acid;
(4)600 g of REY molecular sieve is added with 600 g of water and pulped for standby;
(5) and (3) adding the serosity of (1), (2), (3) and (4) into the mixture in a parallel flow manner for mixing and pulping, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, performing spray drying, adding 3 g of zinc hydroxide during roasting, washing and drying, and marking a sample as Cat-4.
Example 5
(1) Weighing 700 g of kaolin and 250 g of phosphorus-aluminum adhesive (the phosphorus-aluminum ratio is 6.0), adding 500 g of water, controlling the solid content of the slurry to be more than or equal to 50%, mixing and pulping for 16 hours, and controlling the temperature of the slurry to be between 80 and 90 ℃;
(2) weighing 200 g of alumina sol and 0.007 g of polyethylene glycol, adding the polyethylene glycol into the alumina sol, and uniformly stirring for later use;
(3) weighing 360 g of pseudo-boehmite, adding 350 g of water, pulping, and adding 0.5 g of boric acid;
(4)600 grams of REY molecular sieve is added with 600 grams of water and beaten for standby;
(5) and (3) adding the serous fluid of (1), (2), (3) and (4) into the mixture in a cocurrent flow manner, mixing and pulping, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, performing spray drying, adding 5 g of zinc hydroxide during roasting, washing and drying, and marking a sample as Cat-5.
Comparative example
(1) Weighing 840 g of kaolin and 200 g of alumina sol, adding 1600 g of water, mixing and pulping for 16 hours;
(2) weighing 600 g of REY molecular sieve, adding 1000 g of water, and pulping for later use;
(3) weighing 360 g of pseudo-boehmite;
(4) adding the molecular sieve slurry obtained in the step (2) into the slurry obtained in the step (1) for mixing and pulping, pouring the pseudoboehmite weighed in the step (3) into the mixed slurry for uniformly stirring, supplementing water, keeping the solid content at about 35%, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, and performing spray granulation, washing and drying to obtain a sample labeled as Cat-DB.
The results of the analysis and test of the physicochemical indexes of the catalyst prepared above are shown in table 1:
TABLE 1 catalyst physicochemical data
As can be seen from Table 1, the specific surface area of the catalyst prepared by the method is 20-40m higher than that of the normal catalyst 2 G, and this is mainly a result of the increase in the specific surface of the substrate, the variation in the specific surface of the micropores is small.
Adopting an iron naphthenate saturated impregnation method to carry out organic iron pollution impregnation on the catalyst, wherein the target iron amount is 12000ppm, carrying out hydrothermal aging inactivation treatment on the impregnated sample by using a hanging basket hydrothermal aging device, and carrying out aging treatment for 10 hours under the hydrothermal aging condition of 760 ℃ and 100% of water vapor. Finally, the treated catalyst samples are respectively placed in ACE-AP for performance evaluation, the loading amount of the catalyst is 9 g, the reaction temperature is 527 ℃, and the catalyst-oil ratio is 6. The composition of the raw material oil used for evaluation is shown in Table 2, and the ACE evaluation results are shown in Table 3.
TABLE 2 basic Properties of the stock oils
TABLE 3 evaluation results of catalysts
As can be seen from the evaluation results in Table 3, the catalysts of examples 1-5 have conversion rates significantly higher than those of comparative examples 0.4-1.3 percentage points, and show better iron pollution resistance and excellent product selectivity.
Claims (6)
1. A preparation method of an iron pollution resistant catalytic cracking catalyst comprises the following specific steps:
(1) mixing kaolin and phosphorus-aluminum glue, pulping, controlling the solid content to be more than or equal to 50%, and stirring for more than or equal to 6 hours;
(2) adding polyethylene glycol into the alumina sol, and uniformly stirring for later use;
(3) adding water into pseudo-boehmite for pulping, and adding boric acid for pre-acidification;
(4) adding water into REY molecular sieve, pulping, and stirring uniformly for later use;
(5) and (3) adding the slurry in the steps (1), (2), (3) and (4) into a pulping barrel in a cocurrent flow manner, uniformly stirring, adding hydrochloric acid for acidification, controlling the pH value to be 2.2-3.0, and finally performing spray granulation, roasting, washing and drying to obtain a finished product.
2. The method of claim 1, wherein: in the step (1), the adding proportion of the phosphor-aluminum glue is P 2 O 5 Accounting for 5-10 wt% of the dry basis of the finished product.
3. The system of claim 1The preparation method is characterized by comprising the following steps: in the step (1), the composition of the phosphor-aluminum paste is P 2 O 5 With Al 2 O 3 The molar ratio is 4.5-10.
4. The method of claim 1, wherein: the molecular weight of the polyethylene glycol in the step (2) is 1000-2000g/mol, and the adding proportion accounts for Al 2 O 3 0.001 to 0.01 wt% of the aluminum sol.
5. The method of claim 1, wherein: the adding proportion of the boric acid in the step (3) is H 3 BO 3 Calculated as Al 2 O 3 0.1-0.3 wt% of pseudoboehmite.
6. The method of claim 1, wherein: in the step (5), an opening is added on a pipeline which is connected with the roasting furnace at the bottom of the spraying tower so as to realize the purpose of continuously adding zinc hydroxide, wherein the adding proportion of the zinc hydroxide is 0.1-0.5 wt% of the dry basis of the finished product calculated by ZnO.
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