CN116273142A - Preparation method of diesel catalytic cracking catalyst for increasing yield - Google Patents
Preparation method of diesel catalytic cracking catalyst for increasing yield Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002283 diesel fuel Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 11
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 abstract description 9
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 9
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 7
- 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 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims 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 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 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 description 7
- 238000004537 pulping Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000000295 fuel oil Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical class [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 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
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
Abstract
The invention discloses a preparation method of a diesel catalytic cracking catalyst for increasing yield, which uses polybasic acid to treat halloysite, and adds aluminum hydroxide powder to adjust slurry environment, and then adds active components and a certain proportion of binder. The catalyst prepared by the method has obvious diesel oil yield increasing characteristic, and provides a new choice for the synergy of refineries.
Description
Technical Field
The invention relates to a preparation method of a diesel catalytic cracking catalyst for increasing yield, belonging to the field of catalyst preparation.
Background
Catalytic cracking is an important means for crude oil processing, and more than 70% of gasoline and more than 30% of diesel oil in China are derived from catalytic cracking. The increasing worldwide demand for clean oil products has led to a diesel trend in the fuels of internal combustion engines. Compared with gasoline engines, diesel engines have the advantages of high power, high fuel oil heat efficiency, long service life, good starting performance, low carbon monoxide and hydrocarbon emissions, low oil consumption and the like, so that how to generate more diesel oil in the catalytic cracking process is a technical problem which needs to be solved urgently, and increasing the yield of diesel oil is an advantageous measure for the refinery to maximize the benefit.
In order to achieve the purpose of increasing the yield of diesel oil, the production process can be realized through the aspects of raw material configuration, product segmentation, device technology, process transformation and the like. The catalyst can also be used as a special catalyst, and the multi-diesel catalyst in China at present is mainly a series of catalysts for multi-diesel oil production such as MLC-500, DMC-2, CC-20D and the like which are developed by Dan Ke institute, and has better application effect. The agent can be used as a catalyst alone or as an auxiliary agent, and has a certain effect in increasing the yield of light oil. The catalyst has the defects that the acid and alkali modification is carried out on different components, the specific surface area is adjusted, the pore structure and the size distribution are adjusted, and the like, but basically, the diesel oil yield is difficult to be greatly improved, the preparation process is complex, and the like.
CN201110332284 discloses a catalytic cracking catalyst for producing diesel oil with high yield of alkali nitrogen, which can exhibit higher catalytic cracking activity in the process of catalytic cracking heavy oil, and can obtain higher conversion rate and higher diesel oil yield. The catalyst comprises cracking active components, mesoporous silica-alumina material, a binder and clay.
CN103506148A no more than 30wt% ultrastable Y molecular sieve containing magnesium on a dry basis, 10 wt% to 70 wt% clay on a dry basis, and 10 wt% to 40 wt% inorganic oxide binder on an oxide basis; the unit cell constant of the modified Y-type molecular sieve is 2.420-2.440 nm, the weight percentage of P is 0.05-6%, the weight percentage of RE2O3 is 0.03-10%, the alumina is less than 22%, and the specific hydroxyl nest concentration is less than 0.35mmol/g. The catalytic cracking catalyst provided by the invention can reduce raw coke, improve the utilization rate of heavy oil and improve the yield of diesel oil.
Cn201410082884.X discloses a heavy oil catalytic cracking catalyst for producing more diesel oil and a preparation method thereof. The method comprises the steps of pulping and uniformly mixing a molecular sieve, pseudo-boehmite, clay, inorganic acid and deionized water, adding or not adding aluminum sol at the same time to prepare catalyst slurry, spray-drying, roasting, exchanging and washing with an ammonium sulfate and ammonium dihydrogen phosphate solution, and finally drying to obtain the catalyst. The method can effectively control the peptization degree of the pseudo-boehmite so as to avoid the influence of the fluctuation of the pore volume of the catalyst by the pseudo-boehmite acid. Compared with the prior art, the method provided by the invention can increase the pore volume of the catalyst and improve the heavy oil cracking capacity and the diesel oil yield of the catalyst.
CN200510084253.2 discloses a catalytic cracking promoter for producing more diesel oil and its preparation method, which is prepared by roasting spray microsphere containing kaolin, pseudo-boehmite and water glass at high temperature above 900 deg.c, extracting pore canal with strong alkali such as sodium hydroxide, and finally loading promoter prepared from phosphorus and rare earth, wherein the promoter does not contain any kind of zeolite component, sodium oxide is less than 0.6%, and at the same time, contains 1-3.5% phosphorus and 1-5% rare earth oxide by mass percent. By adding a certain amount of the cocatalyst, the diesel oil yield of the FCC catalytic device can be improved, the product distribution can be improved, and the utilization rate of the existing catalyst variety can be improved under the condition that the catalyst originally adopted by the oil refining device is not changed. In addition, the cocatalyst has the characteristics of simple preparation process, low cost and the like.
CN201810355600.8 discloses a catalytic cracking catalyst for producing more diesel oil and a preparation method thereof, and the preparation method comprises the following steps: (1) Mixing and pulping raw materials and deionized water to prepare slurry; (2) spray-drying the slurry, followed by calcination and washing; wherein the raw materials comprise boron-containing substances other than boron phosphates, molecular sieves, clay minerals, and a fourth component comprising binding action. The catalyst of the invention has high diesel oil yield, heavy metal pollution resistance and simple preparation process.
In addition, to obtain higher diesel yields, heavier feed oils are required, which generally contain higher heavy metals, basic nitrogen and sulfides, and the catalyst is susceptible to poisoning and deactivation, and the sulfides in the flue gas are susceptible to exceeding standards, so that the influence of these adverse factors should be considered in designing the catalyst.
The invention comprises the following steps:
in order to solve the defects of the technology, the invention provides a preparation method of a high-yield diesel catalytic cracking catalyst, which comprises the following specific synthesis steps:
(1) Adding water into the multi-water kaolin, pulping, adding a certain proportion of polybasic acid, controlling the temperature to rise, and stirring for more than 3 hours;
(2) The aluminum hydroxide powder with a certain proportion in the slurry is stirred for more than 1 hour by controlling the temperature rise;
(3) Adding REUSY molecular sieve and aluminum sol in a certain proportion twice, wherein the adding interval of the two materials is more than 10 minutes;
(4) And (3) immediately spray-drying after all materials are added, controlling the temperature of a spray inlet and a spray outlet, roasting and washing the obtained particles, and drying to obtain the target.
The halloysite in the step (1) requires a tubular structure of more than 70% and a specific surface of more than 60m 2 Per g, fe content is less than 1.0wt%; the polybasic acid in the step (1) can be phosphoric acid, lactic acid and/or citric acid, and the addition amount is 10-25wt% of the dry basis of the halloysite; the addition amount of the aluminum hydroxide powder in the step (2) is 10-20wt% of the polybasic acid;
REUSY molecular sieve RE in step (3) 2 O 3 ＝4-10wt％，
The addition proportion is 20-30wt% of the catalyst dry basis;
the addition amount of the aluminum sol in the step (3) is 3-5wt% of the dry catalyst based on aluminum oxide;
in the step (4), the inlet temperature is required to be lower than 350 ℃ and the outlet temperature is required to be 120-150 ℃.
The invention has the advantages that:
(1) The REUSY molecular sieve is used as an active component, and the molecular sieve has lower rare earth content and lower hydrogen transfer activity by adopting a lower adding proportion, so that excessive cracking is prevented, and the invention is more beneficial to the production of diesel oil and the reduction of coke.
(2) The multi-water kaolin reacts with the polybasic acid, a part of the multi-water kaolin plays a role in reaming and a part of the multi-water kaolin plays a role in bonding, and when the phosphoric acid is used for treatment, excessive phosphoric acid forms phosphorus hydroxyl on the surface of the carrier, so that the multi-water kaolin is a medium strong acid, is beneficial to cracking of heavy oil macromolecules and can control the reaction depth; when lactic acid or citric acid is used, the lactic acid or citric acid is adsorbed on a carrier, and can be roasted after spray granulation, so that a certain proportion of holes penetrating to the surface of particles are left, the diffusion of heavy oil macromolecules is facilitated, and excessive cracking is avoided.
(3) The aluminum hydroxide powder has two functions, namely, the reaction generates substances with a binding function, and the function of adjusting the pH value of the slurry is achieved, so that the phenomenon that the molecular sieve structure collapses due to excessive dealumination when REUSY molecular sieve is added due to the too low pH value of the slurry is avoided.
The specific embodiment is as follows:
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.
Halloysite: burning 33.0%;
phosphoric acid: 75%;
aluminum hydroxide powder: 63.5% of Al 2 0 3 Counting;
REUSY-1：RE 2 O 3 =9.1%, 25% burn;
REUSY-2：RE 2 O 3 =6.5%, 25% burn;
REUSY-1：RE 2 O 3 =4.3%, 25% burn;
aluminum sol: 21.2%, by Al 2 0 3 Counting;
catalyst evaluation:
using an ACE evaluation unit, the catalyst was subjected to pretreatment at 800 ℃ for 17 hours with 100% steam aging, 9g of the catalyst was added, the reaction temperature was 505 ℃ and the catalyst to oil ratio was 9.
The data for evaluating the raw oil are as follows:
table 1 evaluation of raw oil data used
Example 1:
(1) 855.2g of the halloysite is added with 1490g of water for pulping, 92g of 75% phosphoric acid solution is added, slow addition or cooling measures are adopted, the temperature rise is controlled to be not more than 5 ℃, and stirring is carried out for more than 3 hours;
(2) 13.1g of aluminum hydroxide powder is added into the slurry, the temperature is controlled to rise, and stirring is carried out for more than 1 hour;
(3) REUSY molecular sieve and alumina sol are added twice, the addition amounts are 266.7g and 141.5g respectively, and the addition interval of the two materials is more than 10 minutes when half of the total amount is added each time;
(4) And (5) immediately spray-drying after all materials are added, controlling the temperature of a spray inlet and a spray outlet, roasting, washing and drying the obtained particles, and marking the particles as ZC-1.
Example 2:
(1) 698.5g of the halloysite with 1500g of water is added for pulping, 106.7g of 75 percent phosphoric acid solution is added, slow addition or cooling measures are adopted, the temperature rise is controlled to be not more than 8 ℃, and stirring is carried out for more than 3 hours;
(2) 18.9g of aluminum hydroxide powder is added into the slurry, the temperature is controlled to rise, and stirring is carried out for more than 1 hour;
(3) REUSY molecular sieve and alumina sol are added twice, the addition amounts are 333.3g and 188.7g respectively, and the addition interval of the two materials is more than 10 minutes when half of the total amount is added each time;
(4) And (5) immediately spray-drying after all materials are added, controlling the temperature of a spray inlet and a spray outlet, roasting, washing and drying the obtained particles, and marking the particles as ZC-2.
Example 3:
(1) 546.3g of the halloysite with 1530g of water is added for pulping, 117.3g of 75 percent phosphoric acid solution is added, slow addition or cooling measures are adopted, the temperature rise is controlled to be not more than 10 ℃, and stirring is carried out for more than 3 hours;
(2) 24.9g of aluminum hydroxide powder is added into the slurry, the temperature is controlled to rise, and stirring is carried out for more than 1 hour;
(3) REUSY molecular sieve and alumina sol are added twice, the addition amounts are 400g and 235.8g respectively, and the addition interval of two materials is more than 10 minutes when half of the total amount is added each time;
(4) And (5) immediately spray-drying after all materials are added, controlling the temperature of a spray inlet and a spray outlet, roasting, washing and drying the obtained particles, and marking the particles as ZC-3.
The four catalyst samples were aged with 2 stimulation diesel catalysts available on the market, and compared with ACE for evaluation, with the following data:
table 2ACE evaluation of product distribution
| Catalyst numbering | ZC-1 | ZC-2 | ZC-3 | Comparative 1 | Comparative-2 |
| Dry gas | 2.22 | 2.27 | 2.09 | 2.35 | 2.65 |
| Liquefied gas | 8.32 | 10.28 | 9.32 | 12.06 | 13.15 |
| Gasoline | 36.1 | 38.07 | 36.05 | 39.96 | 40.18 |
| Diesel oil | 33.45 | 30.74 | 33.26 | 26.49 | 26.08 |
| Heavy oil | 12.98 | 11.87 | 12.14 | 12.05 | 10.62 |
| Coke | 6.93 | 6.77 | 7.14 | 7.09 | 7.32 |
| Conversion rate | 53.57 | 57.39 | 54.6 | 61.46 | 63.3 |
| Diesel selectivity | 0.62 | 0.54 | 0.61 | 0.43 | 0.41 |
As can be seen from the above table, the samples obtained in the examples all significantly improved the diesel yield compared to the comparative samples.
Claims (7)
1. A method for preparing a catalyst for increasing the yield of diesel oil catalytic cracking, which comprises the following steps:
(1) Adding water into the multi-water kaolin, pulping, adding a certain proportion of polybasic acid, controlling the temperature to rise, and stirring for more than 3 hours;
(2) The aluminum hydroxide powder with a certain proportion in the slurry is stirred for more than 1 hour by controlling the temperature rise;
(3) Adding REUSY molecular sieve and aluminum sol in a certain proportion twice, wherein the adding interval of the two materials is more than 10 minutes;
(4) And (3) immediately spray-drying after all materials are added, controlling the temperature of a spray inlet and a spray outlet, roasting and washing the obtained particles, and drying to obtain the target.
2. The process according to claim 1, wherein the halloysite in step (1) has a tubular structure of more than 70% and a specific surface of more than 60m 2 And/g, the Fe content is less than 1.0wt%.
3. The process according to claim 1, wherein the polyacid in step (1) is phosphoric acid, lactic acid and/or citric acid in an amount of 10 to 25% by weight based on the dry weight of the halloysite.
4. The process according to claim 1, wherein the aluminum hydroxide powder is added in the amount of 10 to 20wt% based on the polybasic acid in the step (2).
5. The process according to claim 1, wherein in step (3) REUSY molecular sieve RE 2 O 3 ＝4-10wt％，
The addition proportion is 20-30wt% of the catalyst dry basis.
6. The process according to claim 1, wherein the alumina sol is added in step (3) in an amount of 3 to 5% by weight based on the dry catalyst on the basis of alumina.
7. The process according to claim 1, wherein the inlet temperature in step (4) is lower than 350℃and the outlet temperature is 120-150 ℃.
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