CN107970971A - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents

A kind of catalytic cracking catalyst and preparation method thereof Download PDF

Info

Publication number
CN107970971A
CN107970971A CN201610921147.3A CN201610921147A CN107970971A CN 107970971 A CN107970971 A CN 107970971A CN 201610921147 A CN201610921147 A CN 201610921147A CN 107970971 A CN107970971 A CN 107970971A
Authority
CN
China
Prior art keywords
molecular sieve
acid
weight
ratio
rare earth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610921147.3A
Other languages
Chinese (zh)
Other versions
CN107970971B (en
Inventor
庄立
罗斌
罗一斌
朱玉霞
欧阳颖
陈振宇
刘建强
任飞
舒兴田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610921147.3A priority Critical patent/CN107970971B/en
Publication of CN107970971A publication Critical patent/CN107970971A/en
Application granted granted Critical
Publication of CN107970971B publication Critical patent/CN107970971B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention provides a kind of catalytic cracking catalyst and preparation method thereof, and with dry basis, the catalyst contains the natural mineral matter of the Y molecular sieve of the phosphorous and rare earth of 25 75 weight %, the inorganic oxide binder of 10 30 weight % and 15 65 weight %；Wherein, the described phosphorous and cell parameter of the Y molecular sieve of rare earth is 24.35 24.55 angstroms；The phosphorus content of the molecular sieve is 0.3 10 heavy %；The content of rare earth of the molecular sieve is 0.5 19 heavy %；The Al distributed constants D of the molecular sieve meets：0.4≤D≤0.9；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25 65%；The molecular sieve strong acid acid amount account for total acid content ratio be 20 60%, B acid acid amount with L acid acid amount the ratio between be 20 100.With excellent heavy oil conversion performance, the gasoline and yield of liquefied gas of higher, lower coke yield when catalytic cracking catalyst provided by the invention is used for heavy oil catalytic cracking.

Description

A kind of catalytic cracking catalyst and preparation method thereof
Technical field
The present invention relates to a kind of catalytic cracking catalyst and preparation method thereof.
Background technology
Catalytic cracking (FCC) is important crude oil secondary processing process, and very important status is occupied in petroleum refining industry. In catalytic cracking process, the residual oil of heavy end such as vacuum distillate or more heavy constituent reacts in the presence of a catalyst, The high value added products such as liquefied gas, gasoline, diesel oil are converted into, usually require to use with high cracking activity in this process Catalysis material.Molecular sieve with Shape-selective, higher ratio surface and stronger acidity due to being widely used in oil refining In system and processing industry.Y type molecular sieve (HY, REY, USY) is since the sixties in last century of use first, and just always catalysis is split Change, the chief active constituent element of hydrocracking catalyst.However, with the aggravation of crude oil heaviness, the polycyclic compound in raw material Content dramatically increases, and the Y type molecular sieve aperture as predominant cracking group member only has 0.74nm, is evaporated for heavys such as process residual oils Point, the accessibility of catalyst active center will become polycyclic compound contained therein (such as polycyclic aromatic hydrocarbon, polycyclic naphthene hydrocarbon) The major obstacle of cracking；The presence of molecular sieve surface acidity so that the heavy oil molecules in duct cannot be entered in molecular sieve outer surface Occur to react without selection, influence product distribution.
Poromerics aperture is smaller, surface has more polyoxybiontic weakness in order to overcome, rich in mesoporous catalysis material Synthesis is increasingly subject to the attention of people.
A kind of preparation side of the Y type molecular sieve of containing mesopore is disclosed in United States Patent (USP) US 5069890 and US 5087348 Method, main process are:Using commercially available USY as raw material, in the atmosphere of 100% vapor, 24h is handled at 760 DEG C.This method Obtained Y type molecular sieve mesopore volume increases to 0.14mL/g by 0.02mL/g, but crystallinity drops to 70% by 100%, than Surface area is by 683m2/ g is reduced to 456m2/ g, sour density more drop to 6% by 28.9%.
In the method for the disclosed Y type molecular sieves for preparing containing mesopore of United States Patent (USP) US 5601798, using HY or USY as original Material, is placed in autoclave and NH4NO3Solution or NH4NO3With HNO3Mixed solution mix, in 115 DEG C~250 DEG C of temperature Lower processing 2h~20h, the mesopore volume of obtained Y type molecular sieve up to 0.2mL g~0.6mL g, but crystallinity and compare surface Product is all decreased significantly.
Chinese patent CN101722022 discloses a kind of alkali treatment modifying method of Y type molecular sieve, including according to molecular sieve (butt)：Highly basic：Distilled water=(0.1~2)：(0.05~2)：The mass ratio of (4~15) is by Y type molecular sieve and strong alkali aqueous solution Mashing is uniformly mixed, 0.1~24h of alkali process at 0~120 DEG C, and obtained molecular sieve has more compared with parent Y molecular sieve High N2Adsorbance.
The method that skeleton silicon-rich Y-shaped molecular sieve is prepared disclosed in Chinese patent CN 101723399, first with lye to NaY Molecular sieve carries out desiliconization pretreatment, then ammonium exchange, dealumination complement silicon processing are carried out to the molecular sieve after alkali process, obtained Y types point Son sieve is mesoporous to be increased, but unobvious.
Chinese patent CN103172082 discloses a kind of preparation method of the Y type molecular sieve of containing mesopore, first to sodium form Y Molecular sieve carries out ammonium exchange, is handled followed by aqueous solutions of organic acids, and the molecular sieve after to acid treatment carries out NaOH processing, Finally handled using aqueous ammonium nitrate solution, obtain the Y type molecular sieve of containing mesopore.Obtained Y type molecular sieve, containing abundant micro- Hole, mesoporous pore volume can arrive 0.5mL/g~1.5mL/g.
Chinese patent CN104760973 discloses Y type molecular sieve of the mesoporous content of a kind of superelevation and preparation method thereof, first Y-type zeolite is pre-processed into 1~5h at 300~600 DEG C；It is cooled to 200~600 DEG C；In dried over anhydrous environment, to by pre- It is passed through in the y-type zeolite of processing by the dry gas of dealumination complement silicon saturation, reacts 0.5~7h, obtain crude product；Or anhydrous dry Under dry environment, while temperature to be at the uniform velocity warming up to 250~700 DEG C, it is passed through into the y-type zeolite by pretreatment and is mended by dealuminzation The dry gas of silicon saturation, reacts 0.5~7h, obtains crude product；Crude product carries out acid treatment；To the crude product after acid treatment into Row alkali process, obtains Y type molecular sieve.Y type molecular sieve made from this method has the mesoporous content of superelevation, but micro pore volume is relatively low.
The content of the invention
The object of the present invention is to provide a kind of catalytic cracking catalyst and preparation method thereof, catalytic cracking provided by the invention With excellent heavy oil conversion performance when catalyst is used for heavy oil catalytic cracking, the gasoline and yield of liquefied gas of higher are lower Coke yield.
To achieve these goals, the present invention provides a kind of catalytic cracking catalyst, with dry basis, the catalyst The Y molecular sieve of phosphorous and rare earth containing 25-75 weight %, the inorganic oxide binder of 10-30 weight % and 15-65 weights Measure the natural mineral matter of %；Wherein, the described phosphorous and cell parameter of the Y molecular sieve of rare earth is 24.35-24.55 angstroms；With P2O5 Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.3-10 weights %；With RE2O3Count and with molecule On the basis of the butt weight of sieve, the content of rare earth of the molecular sieve is 0.5-19 weights %；The Al distributed constants D of the molecular sieve expires Foot：0.4≤D≤0.9, wherein, D=Al (S)/Al (C), Al (S) represent the zeolite crystal measured using TEM-EDS methods The inside H in crystal face edge represents to survey using TEM-EDS methods apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C) The outside H of the geometric center of crystal face described in fixed zeolite crystal apart from interior any aluminium content for being more than 100 square nanometers regions, its Described in H be the crystal face edge point to the crystal face geometric center distance 10%；The mesopore volume of the molecular sieve accounts for always The ratio of pore volume is 25-65%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 20-60%, B acid acid amounts and L The ratio between sour amount is 20-100；The molecular sieve27In Al MAS H NMR spectroscopies, chemical shift is 60ppm ± 2ppm resonance signals Peak area and chemical shift be that the ratio between peak area of 55ppm ± 2ppm resonance signals is (1.5-5)：1, chemical shift for 0 ± The ratio that the peak area of 2ppm resonance signals accounts for total peak area is not more than 5%.
Preferably, the cell parameter of the molecular sieve is 24.40-24.52 angstroms；With P2O5Count and with the dry basis of molecular sieve On the basis of amount, the phosphorus content of the molecular sieve is 1-8 weights %；With RE2O3Count and on the basis of the butt weight of molecular sieve, it is described The content of rare earth of molecular sieve is 3-16 weights %；The Al distributed constants D of the molecular sieve meets：0.55≤D≤0.8；The molecule The ratio that the mesopore volume of sieve accounts for total pore volume is 30-61%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 25- The ratio between 55%, B acid acid amount and L acid acid amounts are 35-75；The molecular sieve27In Al MAS H NMR spectroscopies, chemical shift 60ppm The peak area of ± 2ppm resonance signals and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signals is (2-4)：1, change The ratio that displacement study accounts for total peak area for the peak area of 0 ± 2ppm resonance signals is not more than 3%.
Preferably, the rare earth is selected from least one of lanthanum, cerium, praseodymium and neodymium.
Preferably, the natural mineral matter is included selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave rod At least one of stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, the inorganic oxide binder include choosing At least one of autoxidation silicon, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, which includes：It will be used to prepare and urge It is beaten and is spray-dried after raw material and the water mixing of fluidized cracking catalysts；Wherein, included with dry basis, the raw material The precursor and 15-65 of the Y molecular sieve of the phosphorous and rare earth of 25-75 weight %, the inorganic oxide binder of 10-30 weight % The natural mineral matter of weight %；The described phosphorous and cell parameter of the Y molecular sieve of rare earth is 24.35-24.55 angstroms；With P2O5Meter is simultaneously On the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.3-10 weights %；With RE2O3Count and with molecular sieve On the basis of butt weight, the content of rare earth of the molecular sieve is 0.5-19 weights %；The Al distributed constants D of the molecular sieve meets： 0.4≤D≤0.9, wherein, D=Al (S)/Al (C), Al (S) represent the crystalline substance of the zeolite crystal using TEM-EDS methods measure Edge inside H in face represents to measure using TEM-EDS methods apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C) Zeolite crystal described in crystal face the outside H of geometric center apart from interior any aluminium content for being more than 100 square nanometers regions, wherein The H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The mesopore volume of the molecular sieve accounts for total hole The ratio of volume is 25-65%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 20-60%, B acid acid amounts and L acid The ratio between acid amount is 20-100；The molecular sieve27In Al MAS H NMR spectroscopies, chemical shift is 60ppm ± 2ppm resonance signals Peak area and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signals is (1.5-5)：1, chemical shift for 0 ± The ratio that the peak area of 2ppm resonance signals accounts for total peak area is not more than 5%.
Preferably, the described phosphorous and Y molecular sieve of rare earth preparation process includes：A, NaY molecular sieve is subjected to ammonium exchange Processing, and after being filtered and being washed, obtain ammonium and exchange molecular sieve；Wherein, molecular sieve is exchanged in terms of sodium oxide molybdena and with the ammonium Butt weight on the basis of, the sodium oxide content that the ammonium exchanges molecular sieve is less than 5 heavy %；B, gained ammonium in step a is exchanged Molecular sieve carries out calcination process, obtains roasting molecular sieve；C, gained roasting molecular sieve in step b is used four in anhydrous conditions Silicon chloride gas carries out dealumination complement silicon processing, obtains dealumination complement silicon molecular sieve；D, gained dealumination complement silicon molecular sieve in step c is existed The first dealumination treatment is carried out in the acid solution be made of organic acid and inorganic acid, and after being filtered and being washed, it is de- to obtain first Aluminum molecular screen；E, the first dealuminzation molecular sieve of gained in step d is subjected to alkali process in inorganic alkali solution, and is filtered and washed After washing, alkali process molecular sieve is obtained；F, by gained alkali process molecular sieve in step e by fluosilicic acid, organic acid and inorganic acid group Into Compound-acid dealuminzation agent solution in carry out the second dealumination treatment, and after being filtered and being washed, obtain the second dealuminzation molecular sieve； G, the second dealuminzation molecular sieve of gained in step f is soaked in the dipping solution containing phosphorus-containing compound and compounds containing rare earth Stain processing, and filtered, washed and in steam atmosphere after progress hydrothermal calcine processing, obtain described phosphorous and rare earth Y molecular sieve.
Preferably, the condition of calcination process includes described in step b：Calcination atmosphere is air atmosphere, temperature 300-600 DEG C, when the time is 0.5-4 small.
Preferably, the condition of the processing of dealumination complement silicon described in step c includes：Temperature is 200-600 DEG C, time 0.5-4 Hour.
Preferably, organic acid described in acid solution described in step d be selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and At least one of sulfosalicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of the first dealumination treatment includes described in step d：With the molecular sieve of dry basis, organic acid Weight ratio with inorganic acid is 1：(0.03-0.3):(0.02-0.4)；First dealumination treatment temperature is 25-100 DEG C, and first is de- When aluminium processing time is 0.5-6 small.
Preferably, inorganic alkali solution described in step e is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide At least one of solution and ammonium hydroxide.
Preferably, the condition of alkali process includes described in step e：With the weight of the molecular sieve of dry basis and inorganic base The ratio between be 1：(0.02-0.6)；Its alkali purification temp is 25-100 DEG C, when the alkali process time is 0.5-6 small.
Preferably, organic acid described in Compound-acid dealumination agent described in step f is selected from ethylenediamine tetra-acetic acid, oxalic acid, lemon At least one of lemon acid and sulfosalicylic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the condition of the second dealumination treatment includes described in step f：With the molecular sieve of dry basis, fluosilicic acid, The weight ratio of organic acid and inorganic acid is 1：(0.03-0.3):(0.05-0.3):(0.05-0.25)；Second dealumination treatment temperature Spend for 25-100 DEG C, when the second dealumination treatment time was 0.5-6 small.
Preferably, phosphorus-containing compound described in step g is in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate At least one, the compounds containing rare earth be selected from chlorate and/or nitric acid containing at least one of lanthanum, cerium, praseodymium and neodymium Salt.
Preferably, the condition of impregnation includes described in step g：With P2O5The phosphorus-containing compound of meter, with RE2O3Meter Compounds containing rare earth and using the weight ratio of the molecular sieve of dry basis as (0.001-0.1)：(0.11-0.32)：1, the leaching Stain solution with using the weight ratio of the molecular sieve of dry basis as (6-25)：1；The temperature of the impregnation is 30-90 DEG C, leaching When the time of stain processing is 0.5-3 small.
Preferably, the condition of the processing of hydrothermal calcine described in step g includes：Temperature is 450-750 DEG C, time 0.5-6 Hour, steam atmosphere is the steam atmosphere of 100 body %.
Preferably, the natural mineral matter is included selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave rod At least one of stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, the predecessor of the inorganic oxide binder Thing is included selected from least one of Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.
With excellent heavy oil conversion performance when catalytic cracking catalyst provided by the invention is used for heavy oil catalytic cracking, more High gasoline and yield of liquefied gas, lower coke yield.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of catalytic cracking catalyst, and with dry basis, the catalyst contains 25-75 weight %'s The phosphorous and natural mineral matter of the Y molecular sieve of rare earth, the inorganic oxide binder of 10-30 weight % and 15-65 weight %, it is excellent Select the Y molecular sieve containing 30-70 weight %, the inorganic oxide binder of 12-28 weight % and the natural ore deposit of 20-55 weight % Material；Wherein, the described phosphorous and cell parameter of the Y molecular sieve of rare earth is 24.35-24.55 angstroms；With P2O5Count and with molecular sieve Butt weight on the basis of, the phosphorus content of the molecular sieve is 0.3-10 weights %；With RE2O3Count and with the butt weight of molecular sieve On the basis of, the content of rare earth of the molecular sieve is 0.5-19 weights %；The Al distributed constants D of the molecular sieve meets：0.4≤D≤ 0.9, wherein, D=Al (S)/Al (C), Al (S) represent using TEM-EDS methods measure zeolite crystal crystal face edge to Interior H represents the molecular sieve using TEM-EDS methods measure apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C) The outside H of geometric center of crystal face described in crystal grain is apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H is The crystal face edge point arrives the 10% of the crystal face geometric center distance；The mesopore volume of the molecular sieve accounts for the ratio of total pore volume Example is 25-65%；The ratio between the ratio that the strong acid acid amount of the molecular sieve accounts for total acid content be 20-60%, and B acid acid amounts and L acid acid are measured For 20-100；The molecular sieve27In Al MAS H NMR spectroscopies, chemical shift for 60ppm ± 2ppm resonance signals peak area with Chemical shift is that the ratio between peak area of 55ppm ± 2ppm resonance signals is (1.5-5)：1, chemical shift is 0 ± 2ppm resonance letters Number peak area account for total peak area ratio be not more than 5%.Preferably, the cell parameter of the molecular sieve is 24.40-24.52 Angstrom；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-8 weights %；With RE2O3Meter is simultaneously On the basis of the butt weight of molecular sieve, the content of rare earth of the molecular sieve is 3-16 weights %；The Al distribution ginsengs of the molecular sieve Number D meets：0.55≤D≤0.8；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30-61%；The molecular sieve Strong acid acid amount to account for the ratio of total acid content be 25-55%, it is 35-75 that the ratio between B acid acid amounts and L acid acid, which are measured,；The molecular sieve27Al In MAS H NMR spectroscopies, chemical shift is the peak area of 60ppm ± 2ppm resonance signals and chemical shift is 55ppm ± 2ppm resonance The ratio between peak area of signal is (2-4)：1, chemical shift accounts for the ratio of total peak area not for the peak area of 0 ± 2ppm resonance signals More than 3%.
According to the present invention, rare earth is well-known to those skilled in the art hydrothermal stability with increase molecular sieve etc. Effect, for example, the rare earth can be selected from least one of lanthanum, cerium, praseodymium and neodymium.
According to the present invention, using TEM-EDS methods measure molecular sieve aluminium content be it is well-known to those skilled in the art, Wherein described geometric center is also well-known to those skilled in the art, can be calculated according to formula, and the present invention is no longer superfluous State, the geometric center of generally symmetrical figure is the intersection point of each opposed apexes line.The crystal face is a face of regular crystal grain, The direction inwardly or outwardly refers both to the direction inwardly or outwardly on the crystal face.
According to the present invention, the mesopore volume of the molecular sieve account for the ratio of total pore volume using nitrogen adsorption desorption method into Row measurement, the mesoporous molecular sieve pore passages for being less than 100 nanometers more than 2 nanometers for aperture；The strong acid acid amount of the molecular sieve accounts for The ratio of total acid content uses NH3- TPD methods measure, and the acid site of the strong acid is NH3It is right that desorption temperature is more than 300 DEG C of institutes The acid site answered；The ratio between B acid acid amount and L acid acid amounts use the infrared acid process of pyridine adsorption to measure；The molecule Sieve27The peak area of resonance signal is calculated using integration method in Al MAS H NMR spectroscopies, before being calculated using integration method It can be determined using swarming fitting process27Each peak of resonance signal in Al MAS H NMR spectroscopies.
According to the present invention, natural mineral matter refers under the comprehensive function of the various materials of the earth's crust what (title geologic process) was formed Natural simple substance or compound, and the distinctive chemical composition with chemical formula expression and relatively-stationary chemical composition, such as can With including selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, swelling At least one of soil and rectorite, inorganic oxide binder refers to the inorganic oxide for playing cohesive each component in the catalyst Thing, such as can include selected from least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, which includes：It will be used to prepare and urge It is beaten and is spray-dried after raw material and the water mixing of fluidized cracking catalysts；Wherein, included with dry basis, the raw material The precursor and 15-65 of the Y molecular sieve of the phosphorous and rare earth of 25-75 weight %, the inorganic oxide binder of 10-30 weight % The natural mineral matter of weight %；The described phosphorous and cell parameter of the Y molecular sieve of rare earth is 24.35-24.55 angstroms；With P2O5Meter is simultaneously On the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 0.3-10 weights %；With RE2O3Count and with molecular sieve On the basis of butt weight, the content of rare earth of the molecular sieve is 0.5-19 weights %；The Al distributed constants D of the molecular sieve meets： 0.4≤D≤0.9, wherein, D=Al (S)/Al (C), Al (S) represent the crystalline substance of the zeolite crystal using TEM-EDS methods measure Edge inside H in face represents to measure using TEM-EDS methods apart from interior any aluminium content for being more than 100 square nanometers regions, Al (C) Zeolite crystal described in crystal face the outside H of geometric center apart from interior any aluminium content for being more than 100 square nanometers regions, wherein The H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The mesopore volume of the molecular sieve accounts for total hole The ratio of volume is 25-65%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 20-60%, B acid acid amounts and L acid The ratio between acid amount is 20-100；The molecular sieve27In Al MAS H NMR spectroscopies, chemical shift is 60ppm ± 2ppm resonance signals Peak area and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signals is (1.5-5)：1, chemical shift for 0 ± The ratio that the peak area of 2ppm resonance signals accounts for total peak area is not more than 5%.
According to the present invention, the described phosphorous and preparation process of the Y molecular sieve of rare earth can include：A, by NaY molecular sieve into The exchange of row ammonium is handled, and after being filtered and being washed, is obtained ammonium and exchanged molecular sieve；Wherein, handed in terms of sodium oxide molybdena and with the ammonium Change on the basis of the butt weight of molecular sieve, the sodium oxide content that the ammonium exchanges molecular sieve is less than 5 heavy %；B, by institute in step a Obtain ammonium and exchange molecular sieve progress calcination process, obtain roasting molecular sieve；C, by gained roasting molecular sieve in step b in anhydrous condition It is lower that dealumination complement silicon processing is carried out using silicon tetrachloride gas, obtain dealumination complement silicon molecular sieve；D, by gained dealumination complement silicon in step c Molecular sieve carries out the first dealumination treatment in the acid solution being made of organic acid and inorganic acid, and after being filtered and being washed, obtains To the first dealuminzation molecular sieve；E, the first dealuminzation molecular sieve of gained in step d is subjected to alkali process in inorganic alkali solution, and carried out After filtering and washing, alkali process molecular sieve is obtained；F, by step e gained alkali process molecular sieve by fluosilicic acid, organic acid and The second dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of inorganic acid composition, and after being filtered and being washed, it is de- to obtain second Aluminum molecular screen；G, it is the second dealuminzation molecular sieve of gained in step f is molten in the dipping containing phosphorus-containing compound and compounds containing rare earth Impregnation is carried out in liquid, and is filtered, washed and in steam atmosphere after progress hydrothermal calcine processing, obtains described contain The Y molecular sieve of phosphorus and rare earth.
According to the present invention, ammonium exchange processing is well-known to those skilled in the art, for example, can press NaY molecular sieve According to molecular sieve：Ammonium salt：Water=1：(0.1-1)：The weight ratio of (5-10) is filtered in room temperature to after when exchange 0.5-2 is small at 100 DEG C. The ammonium salt can be common inorganic ammonium salt, for example, selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the present invention, calcination process can make ammonium exchange molecular sieve take off ammonium, and the condition of calcination process can described in step b With including：Calcination atmosphere is air atmosphere, and temperature is 300-600 DEG C, is preferably 400-550 DEG C, excellent when the time is 0.5-4 small Elect as 1-3.5 it is small when.
According to the present invention, dealumination complement silicon processing is well-known to those skilled in the art, for using tetrachloro at high temperature Element silicon in SiClx substitutes the aluminium element in molecular sieve, for example, the condition of the processing of dealumination complement silicon described in step c includes：Temperature Spend for 200-600 DEG C, be preferably 300-550 DEG C, the time for 0.5-4 it is small when, be preferably 1-3.5 it is small when, preferably 100% four Carried out under silicon chloride atmosphere.
According to the present invention, dealumination treatment is well-known to those skilled in the art that the first dealumination treatment can described in step d Once or several times to carry out, first organic acid can be mixed with the dealumination complement silicon molecular sieve, then by inorganic acid with it is described Dealumination complement silicon molecular sieve mixes；First inorganic acid can also be mixed with the dealumination complement silicon molecular sieve, then by organic acid and institute State the mixing of dealumination complement silicon molecular sieve；Inorganic acid, organic acid can also be mixed with dealumination complement silicon molecular sieve at the same time.Institute in step d It can be at least one in ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid to state organic acid described in acid solution Kind, it is preferably citric acid；Inorganic acid can be selected from least one of hydrochloric acid, sulfuric acid and nitric acid, be preferably nitric acid, described the The condition of one dealumination treatment can be：Using the weight ratio of the molecular sieve of dry basis, organic acid and inorganic acid as 1： (0.03-0.3):(0.02-0.4), is preferably 1：(0.05-0.25):(0.05-0.25)；First dealumination treatment temperature is 25- 100 DEG C, when the first dealumination treatment time was 0.5-6 small.
According to the present invention, alkali process can be used for the part framework silicon atom for removing molecular sieve, produce more second holes, Inorganic alkali solution described in step e can be in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and ammonium hydroxide At least one, be preferably sodium hydroxide solution, the condition of alkali process can include described in step e：With dry basis The weight ratio of molecular sieve and inorganic base is 1：(0.02-0.6), is preferably 1：(0.05-0.4)；Its alkali purification temp is 25-100 DEG C, when the alkali process time is 0.5-6 small.
According to the present invention, although dealumination treatment is well-known to those skilled in the art, do not reported inorganic acid, had Machine acid and fluosilicic acid are used for dealumination treatment together.Second dealumination treatment described in step f can carry out once or several times, can be with First organic acid is mixed with the alkali process molecular sieve, then mixes fluosilicic acid and inorganic acid with the alkali process molecular sieve, Can be with first to add organic acid in alkali process molecular sieve, then by fluosilicic acid and inorganic acid, cocurrent adds at a slow speed, or first adds Enter fluosilicic acid and add inorganic acid, be preferably that cocurrent adds at a slow speed for fluosilicic acid and inorganic acid.Compound-acid dealumination agent described in step f Described in organic acid can be selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, be preferably Oxalic acid, inorganic acid are selected from least one of hydrochloric acid, sulfuric acid and nitric acid, are preferably hydrochloric acid.The bar of second dealumination treatment Part can be：Using the weight ratio of the molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid as 1：(0.03-0.3): (0.05-0.3):(0.05-0.25), is preferably 1：(0.035-0.2):(0.06-0.2):(0.1-0.2)；Second dealumination treatment Temperature is 25-100 DEG C, when the second dealumination treatment time was 0.5-6 small.
According to the present invention, phosphorus-containing compound and compounds containing rare earth are well-known to those skilled in the art, for example, step Phosphorus-containing compound described in g can be selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate, it is described Compounds containing rare earth can be selected from chlorate and/or nitrate containing at least one of lanthanum, cerium, praseodymium and neodymium, be preferably chlorine Change lanthanum and/or lanthanum nitrate.
According to the present invention, impregnation is well-known to those skilled in the art, for example, impregnation described in step g Condition can include：With P2O5The phosphorus-containing compound of meter, with RE2O3The compounds containing rare earth of meter and point with dry basis The weight ratio of son sieve is (0.001-0.1)：(0.11-0.32)：1, be preferably (0.005-0.08)：(0.15-0.23)：1, it is described Dipping solution with using the weight ratio of the molecular sieve of dry basis as (6-25)：1, be preferably (8-15)：1；The temperature of the dipping Spend for 30-90 DEG C, be preferably 60-85 DEG C, when the time of dipping is 0.5-3 small, when being preferably 1-2 small.
According to the present invention, hydrothermal calcine processing is well-known to those skilled in the art, described in step g at hydrothermal calcine The condition of reason can include：Temperature is 450-750 DEG C, is preferably 550-700 DEG C, and when the time is 0.5-6 small, steam atmosphere is The steam atmosphere of 100 body %.
Washing of the present invention is well-known to those skilled in the art, refers generally to wash, it is for instance possible to use 5-10 times 30-60 DEG C of water of molecular sieve elutes molecular sieve.
According to the present invention, the presoma of the inorganic oxide binder refers to be used to generate in catalytic cracking catalyst The preparing raw material of the catalytic cracking catalyst of inorganic oxide binder, for example, can include selected from boehmite, Aluminum sol, At least one of silicon-aluminum sol and waterglass.
The present invention will be further illustrated by embodiment below, but the present invention is not therefore subject to any restriction, Instrument and reagent used by the embodiment of the present invention, unless otherwise instructed, be those skilled in the art's common instrument of institute and Reagent.
The cell parameter of the present invention is measured using RIPP145-90 standard methods, and the assay method is shown in《Petrochemical industry point Analysis method (RIPP test methods)》, Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes.
The P of the present invention2O5、Re2O3, sodium oxide content is measured using GB/T 30905-2014 standard methods.
The TEM-EDS assay methods of the present invention are referring to the research method of solid catalyst, petrochemical industry, 29 (3), and 2000： 227。
Mesoporous pore volume, the assay method of total pore volume of the present invention is as follows：
The AS-3 produced using Quantachrome instrument companies, AS-6 static state n2 absorption apparatus measure.
Instrument parameter：Sample is placed in sample processing system, 1.33 × 10 are evacuated at 300 DEG C-2Pa, heat-insulation pressure keeping 4h, purifies sample.At -196 DEG C of liquid nitrogen temperature, test purification sample is not pressing P/P on year-on-year basis0Under the conditions of to the adsorbance of nitrogen And desorption rate, obtain N2Adsorption-desorption isothermal curve.Then total specific surface area is calculated using two parameter BET formula, micropore compares table Area and mesopore surface area, take than pressing P/P0Less than=0.98 adsorbance is the total pore volume of sample, utilizes BJH formula meters The pore-size distribution of mesoporous part is calculated, and mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous hole are calculated using integration method Volume.
The B acid acid amounts of the present invention and the assay method of L acid acid amounts are as follows：
The FTS3000 type Fourier infrared spectrographs produced using BIO-RAD companies of the U.S..
Test condition：Tabletted be placed in the pond in situ of infrared spectrometer of sample is sealed, is vacuumized at 350 DEG C To 10-3Pa, keeps 1h, the gas molecule of sample surfaces is desorbed totally, is cooled to room temperature.Pressure is imported into pond in situ is The pyridine steam of 2.67Pa, after balancing 30min, is warming up to 200 DEG C, is evacuated to 10 again-3Pa, keeps 30min, is cooled to room Temperature, in 1400-1700cm-1Scanning in wave-number range, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions.Again by infrared suction Sample in receives pond moves to heat-treatment zone, is warming up to 350 DEG C, is evacuated to 10-3Pa, keeps 30min, is cooled to room temperature, records The infrared spectrum of 350 DEG C of pyridine adsorptions.Instrument automatic integration obtains B acid acid amounts and L acid acid amounts.
The assay method of total acid content and strong acid the acid amount of the present invention is as follows：
Using II 2920 temperature programmed desorption instrument of Merck ＆ Co., Inc of U.S. Autochem.
Test condition：Weigh 0.2g samples to be tested and load sample cell, be placed in conductance cell heating furnace, He gas is carrier gas (50mL/ Min), 600 DEG C are warming up to the speed of 20 DEG C/min, purging 60min drives away the impurity of catalyst surface absorption.Then it is cooled to 100 DEG C, constant temperature 30min, switches to NH3- He gaseous mixtures (10.02%NH3+ 89.98%He) absorption 30min, it is further continued for He gas It is steady to baseline to purge 90min, to be desorbed the ammonia of physical absorption.600 DEG C are warming up to 10 DEG C/min heating rates to be taken off It is attached, 30min is kept, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration obtain total acid content and Strong acid acid amount, the acid site of strong acid is NH3Desorption temperature is more than the acid site corresponding to 300 DEG C.
The present invention's27Al MAS NMR are tested using Bruker Avance III 500MHz Nuclear Magnetic Resonance, altogether The peak spectrogram that shakes uses integration method to calculate each peak area after carrying out swarming fitting.
The computational methods of D values are as follows：A crystal grain is chosen in transmission electron microscope and some crystal face of the crystal grain is formed One polygon, there are 10% distance H of geometric center, edge and geometric center to edge point is (different for the polygon Edge point, H values are different), choose respectively any one piece in the inside H distances in the crystal face edge be more than 100 square nanometers regions with And any one piece in the outside H distances of crystal face geometric center is more than 100 square nanometers regions, measures aluminium content, is Al (S1) With Al (C1), and D1=Al (S1)/Al (C1) is calculated, choose different crystal grain respectively and measure 5 times, it is D to calculate average value.
Prepare embodiment 1
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 2h at 600 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 550 DEG C, reaction time 2h；Take above-mentioned molecular sieve 100g (butt quality) plus water The molecular sieve pulp of the weight of solid content 10 % is configured to, citric acid 3g is added in stirring, then adds 400g hydrochloric acid (mass fractions 10%) time 30min, is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Solid content is the molecular sieve pulp of 10 weight %, adds 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, mistake Filter washing is to neutrality；By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 5g oxalic acid, then 50g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) is slowly added dropwise, is warming up to 50 DEG C of constant temperature stirring 1h, filtering Wash to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 6.72gH3PO4(concentration 85%) and Concentration is re chloride (the mixed chlorinated rare earth solution, wherein the La in terms of oxide of 160g/L2O3Account for 36 heavy %, CeO2Account for 64 heavy %, similarly hereinafter) 120mL, it is warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake in 550 DEG C, 100% water vapour atmosphere Middle roasting 6h, obtains sieve sample A, and the physico-chemical property of sieve sample A is listed in table 1.
Prepare comparative example 1
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %；Above-mentioned molecular sieve is taken to roast 1h at 600 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 550 DEG C, reaction time 1h；Take above-mentioned molecular sieve 100g (butt quality) plus water Be beaten solid content is the molecular sieve pulps of 10 weight %, add 10.42gNaOH (purity 96%), be warming up to the stirring of 50 DEG C of constant temperature 0.5h, filtration washing to neutrality；By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, 127g fluorine is slowly added dropwise Silicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is dried to obtain sieve sample DB1, sieve sample The physico-chemical property of DB1 is listed in table 1.
Prepare comparative example 2
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 2h at 500 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 550 DEG C, reaction time 0.5h；Above-mentioned molecular sieve 100g (butt quality) is taken to add Water is configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 5g is added in stirring, then adds 200g hydrochloric acid (mass fractions 10%) time 30min, is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Solid content is the molecular sieve pulp of 10 weight %, adds 31.25gKOH (purity 96%), is warming up to 70 DEG C of constant temperature stirring 0.5h, mistake Filter washing is to neutrality；By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 15g citric acids, Then 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) is slowly added dropwise, is warming up to 50 DEG C of constant temperature stirring 1h, Filtration washing is to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add concentration be 160g/L chlorine Change earth solution 30mL, be warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake in 550 DEG C, 100% water vapour atmosphere 2h is roasted, obtains sieve sample DB2.The physico-chemical property of sieve sample DB2 is listed in table 1.
Prepare embodiment 2
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 3h at 550 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 550 DEG C, reaction time 2h；Take above-mentioned molecular sieve 100g (butt quality) plus water The molecular sieve pulp of the weight of solid content 10 % is configured to, oxalic acid 5g is added in stirring, then adds 200g sulfuric acid (mass fractions 10%) time 30min, is added；30 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Solid content is the molecular sieve pulp of 10 weight %, adds 31.25gKOH (purity 96%), is warming up to 70 DEG C of constant temperature stirring 0.5h, mistake Filter washing is to neutrality；By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 15g ethylenediamine tetraacetics Acetic acid, is then slowly added dropwise 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%), is warming up to 50 DEG C of constant temperature and stirs Mix 1h, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 5.1gNH4H2PO4 With the re chloride 130mL that concentration is 160g/L, 70 DEG C of constant temperature stirring 1.5h, filtration washing, by filter cake 700 are warming up to DEG C, roast 1h in 100% water vapour atmosphere, obtain sieve sample B.The physico-chemical property of sieve sample B is listed in table 1.
Prepare embodiment 3
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 2.5h at 450 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 550 DEG C, reaction time 1.5h；Above-mentioned molecular sieve 100g (butt quality) is taken to add Water is configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 25g is added in stirring, then adds 250g nitric acid (mass fractions 10%) time 30min, is added；90 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten Solid content is the molecular sieve pulp of 10 weight %, adds 35gNaOH (purity 96%), is warming up to 80 DEG C of constant temperature stirring 0.5h, filtering Wash to neutrality；By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 20g oxalic acid, then 105g hydrochloric acid (mass fraction 10%) and 49g fluosilicic acid (concentration 20%) is slowly added dropwise, is warming up to 70 DEG C of constant temperature stirring 1h, filtering Wash to neutrality；By filter cake plus water be beaten solid content 15 weight % molecular sieve pulp, add 7.0gH3PO4(concentration 85%) and Concentration is the re chloride 201mL of 160g/L, is warming up to 90 DEG C of constant temperature stirring 0.5h, filtration washing, by filter cake 700 DEG C, roast 1h in 100% water vapour atmosphere, obtain sieve sample C.The physico-chemical property of sieve sample C is listed in table 1.
Prepare embodiment 4
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 4h at 350 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 250 DEG C, reaction time 3.5h；Above-mentioned molecular sieve 100g (butt quality) is taken to add Water is configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 30g is added in stirring, then adds 100g sulfuric acid (mass fractions 10%) time 1min, is added；55 DEG C of constant temperature stirring 2h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water, which are beaten, to be consolidated Content is the molecular sieve pulp of 10 weight %, adds 41gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, crosses diafiltration Wash to neutrality；By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 30g sulfosalicylic acids, Then 100g hydrochloric acid (mass fraction 10%) and 62g fluosilicic acid (concentration 20%) is slowly added dropwise, is warming up to 50 DEG C of constant temperature stirring 1h, Filtration washing is to neutrality；By filter cake plus water be beaten solid content 20 weight % molecular sieve pulp, add 9.5gH3PO4(concentration 85%) and concentration is the re chloride 180mL of 160g/L, is warming up to 80 DEG C of constant temperature stirring 1h, filtration washing, filter cake is existed 680 DEG C, roast 1h in 100% water vapour atmosphere, obtain sieve sample D.The physico-chemical property of sieve sample D is listed in table 1.
Prepare embodiment 5
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 0.5h at 350 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 250 DEG C, reaction time 0.5h；Above-mentioned molecular sieve 100g (butt quality) is taken to add Water is configured to the molecular sieve pulp of the weight of solid content 10 %, and citric acid 20g is added in stirring, then adds 220g nitric acid mass fractions 10%) time 30min, is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten Solid content is the molecular sieve pulp of 10 weight %, adds 23gLiOH, is warming up to 400 DEG C of constant temperature stirring 2h, filtration washing to neutrality； By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 5g oxalic acid, 148g is then slowly added dropwise Sulfuric acid (mass fraction 10%) and 125g fluosilicic acid (concentration 20%), are warming up to 80 DEG C of constant temperature stirring 1h, filtration washing to neutrality； By filter cake plus water be beaten solid content 15 weight % molecular sieve pulp, add 2.6gH3PO4(concentration 85%) and concentration are 160g/L Re chloride 150mL, be warming up to 80 DEG C of constant temperature stirring 1h, filtration washing, by filter cake in 650 DEG C, 100% water vapour gas 2.5h is roasted in atmosphere, obtains sieve sample E.The physico-chemical property of sieve sample E is listed in table 1.
Prepare embodiment 6
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium content for measuring molecular sieve is small In 5 heavy %.Above-mentioned molecular sieve is taken to roast 0.5h at 550 DEG C.The molecular sieve after roasting is taken to be passed through under dried over anhydrous environment SiCl4Saturation dry gas, reaction temperature are 600 DEG C, reaction time 0.5h；Above-mentioned molecular sieve 100g (butt quality) is taken to add Water is configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 30g is added in stirring, then adds 200g hydrochloric acid (mass fractions 10%) time 30min, is added；75 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten Solid content is the molecular sieve pulp of 10 weight %, adds 46gKOH, is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality； By filter cake plus water be beaten solid content for 20 weight % molecular sieve pulps, in stirring add 6g ethylenediamine tetra-acetic acids, then slowly 90g nitric acid (mass fraction 10%) and 90g fluosilicic acid (concentration 20%) is added dropwise, is warming up to 85 DEG C of constant temperature stirring 4h, filtration washing To neutrality；By filter cake plus water be beaten solid content 15 weight % molecular sieve pulp, add 6.8gH3PO4(concentration 85%) and concentration For the re chloride 220mL of 160g/L, be warming up to 80 DEG C of constant temperature stirring 1h, filtration washing, by filter cake 650 DEG C, 100% 5h is roasted in water vapour atmosphere, obtains sieve sample F.The physico-chemical property of sieve sample F is listed in table 1.
Prepare comparative example 3
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying；Above-mentioned molecular sieve is taken at 600 DEG C Lower roasting 1h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 550 DEG C, reaction time 1h；Take above-mentioned molecular sieve 100g (butt quality) plus water be beaten solid content for 10 weight % molecule screening the pulps Liquid, adds 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；By filter cake plus water Be beaten solid content for 20 weight % molecular sieve pulps, 127g fluosilicic acid (concentration 20%) is slowly added dropwise, is warming up to 50 DEG C of constant temperature Stir 1h, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 6.72gH3PO4 (concentration 85%) and concentration are the RECl of 160g/L3Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 Weight %, CeO2Account for 64 heavy %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing, filter cake is steamed in 550 DEG C, 100% water 6h is roasted in vapour atmosphere, obtains sieve sample DA1, the physico-chemical property of sieve sample DA1 is listed in table 2.
Prepare comparative example 4
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 500 DEG C Lower roasting 2h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 550 DEG C, reaction time 0.5h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecule screening the pulp of the weight of solid content 10 % Liquid, adds oxalic acid 5g in stirring, then add 400g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of perseverances Temperature stirring 1h, filtering are washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water, which are beaten, to be consolidated The molecular sieve pulp of the weight of content 10 %, adds 6.72gH3PO4(concentration 85%) and concentration are the RECl of 160g/L3Solution (mixing Re chloride, wherein the La in terms of oxide2O3Account for 36 heavy %, CeO2Account for 64 heavy %) 120mL, it is warming up to 60 DEG C of constant temperature stirrings 1h, filtration washing, roasts 6h in 550 DEG C, 100% water vapour atmosphere by filter cake, obtains sieve sample DA2, molecular sieve sample The physico-chemical property of product DA2 is listed in table 2.
Prepare comparative example 5
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 300 DEG C Lower roasting 4h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 200 DEG C, reaction time 4h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecular sieve pulp of the weight of solid content 10 %, Oxalic acid 5g is added in stirring, then adds 400g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of constant temperature 1h is stirred, filtering is washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water, which are beaten, to be consolidated Content is the molecular sieve pulp of 20 weight %, and 146g fluosilicic acid (concentration 20%) is added in stirring, is warming up to 50 DEG C of constant temperature stirring 1h, Filtration washing is to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 6.72gH3PO4(concentration 85%) RECl with concentration for 160g/L3Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O336 heavy % are accounted for, CeO2Account for 64 heavy %) 120mL, it is warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake in 550 DEG C, 100% water vapour gas 6h is roasted in atmosphere, obtains sieve sample DA3, the physico-chemical property of sieve sample DA3 is listed in table 2.
Prepare comparative example 6
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 400 DEG C Lower roasting 2h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 300 DEG C, reaction time 4h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecular sieve pulp of the weight of solid content 10 %, Oxalic acid 5g is added in stirring, then adds 400g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of constant temperature 1h is stirred, filtering is washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water, which are beaten, to be consolidated Content is the molecular sieve pulp of 20 weight %, and oxalic acid 12g is added in stirring, then adds 178g hydrochloric acid (mass fraction 10%), is risen Temperature to 50 DEG C of constant temperature stir 1h, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add Enter 6.72gH3PO4(concentration 85%) and concentration are the RECl of 160g/L3Solution (mixed chlorinated rare earth solution, wherein with oxide Count La2O3Account for 36 heavy %, CeO2Account for 64 heavy %) 120mL, it is warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake 550 DEG C, roast 6h in 100% water vapour atmosphere, obtain sieve sample DA4, the physico-chemical property of sieve sample DA4 is listed in table 2.
Prepare comparative example 7
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 350 DEG C Lower roasting 3h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 350 DEG C, reaction time 2h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecular sieve pulp of the weight of solid content 10 %, Oxalic acid 15g is added in stirring, then adds 200g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of constant temperature 1h is stirred, filtering is washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water, which are beaten, to be consolidated Content is the molecular sieve pulp of 20 weight %, and oxalic acid 29g is added in stirring, is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is into Property；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 6.72gH3PO4(concentration 85%) and concentration are The RECl of 160g/L3Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 heavy %, CeO2Account for 64 heavy %) 120mL, is warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, roasts 6h in 550 DEG C, 100% water vapour atmosphere by filter cake, obtain To sieve sample DA5, the physico-chemical property of sieve sample DA5 is listed in table 2.
Prepare comparative example 8
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 350 DEG C Lower roasting 3h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 350 DEG C, reaction time 2h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecular sieve pulp of the weight of solid content 10 %, Oxalic acid 3g is added in stirring, then adds 400g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of constant temperature 1h is stirred, filtering is washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add (10.42gNaOH purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content is 20 weight % Molecular sieve pulp, adds 245g hydrochloric acid (mass fraction 10%) in stirring, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is into Property；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 6.72gH3PO4(concentration 85%) and concentration are The RECl of 160g/L3Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 heavy %, CeO2Account for 64 heavy %) 120mL, is warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, roasts 6h in 550 DEG C, 100% water vapour atmosphere by filter cake, obtain To sieve sample DA6, the physico-chemical property of sieve sample DA6 is listed in table 2.
Prepare comparative example 9
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 350 DEG C Lower roasting 3h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 350 DEG C, reaction time 2h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecular sieve pulp of the weight of solid content 10 %, Oxalic acid 3g is added in stirring, then adds 400g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of constant temperature 1h is stirred, filtering is washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content is 20 weight % Molecular sieve pulp, adds 30g oxalic acid, 100g fluosilicic acid (concentration 20%) is then slowly added dropwise, is warming up to 50 DEG C of constant temperature in stirring Stir 1h, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add 6.72gH3PO4 (concentration 85%) and concentration are the RECl of 160g/L3Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide2O3Account for 36 Weight %, CeO2Account for 64 heavy %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing, filter cake is steamed in 550 DEG C, 100% water 6h is roasted in vapour atmosphere, obtains sieve sample DA7, the physico-chemical property of sieve sample DA7 is listed in table 2.
Prepare comparative example 10
By Y molecular sieve (catalyst asphalt in Shenli Refinery produces, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1： 1:10 ratios are mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, by sample filtering, washing, drying.Above-mentioned molecular sieve is taken at 350 DEG C Lower roasting 3h.The molecular sieve after roasting is taken to be passed through SiCl under dried over anhydrous environment4Saturation dry gas, reaction temperature 350 DEG C, reaction time 2h；Above-mentioned molecular sieve 100g (butt quality) plus water is taken to be configured to the molecular sieve pulp of the weight of solid content 10 %, Oxalic acid 3g is added in stirring, then adds 400g hydrochloric acid (mass fraction 10%), adds time 30min；It is warming up to 75 DEG C of constant temperature 1h is stirred, filtering is washed to filtrate neutrality；By sample plus water be beaten solid content for 10 weight % molecular sieve pulps, add 10.42gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content is 20 weight % Molecular sieve pulp, adds 188g hydrochloric acid (mass fraction 10%), 100g fluosilicic acid (concentration 20%) is then slowly added dropwise in stirring, It is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, Add 6.72gH3PO4(concentration 85%) and concentration are the RECl of 160g/L3Solution (mixed chlorinated rare earth solution, wherein with oxidation Thing meter La2O3Account for 36 heavy %, CeO2Account for 64 heavy %) 120mL, it is warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake 550 DEG C, roast 6h in 100% water vapour atmosphere, obtain sieve sample DA8, the physico-chemical property of sieve sample DA8 is listed in table 2.
For the Y molecular sieve after alkali process desiliconization it can be seen from data in table 2, using single organic acid oxalic acid dealuminzation (DA5), it is compound using single inorganic acid HCl dealumination (DA6) and using organic acid oxalic acid and two kinds of acid of inorganic acid hydrochloric acid (DA4) effectively the Al in molecular sieve can not all be removed, and preferable dealuminzation effect could be obtained after only having used fluosilicic acid Fruit.When fluosilicic acid dealuminzation is used alone (DA3), mesoporous relatively fewer, strong acid proportion in total acid is relatively low, B acid/L acid ratio Example is relatively low.Fluosilicic acid composite organic acid oxalic acid dealuminzation (DA7), can not equally obtain preferable acid distribution.The compound nothing of fluosilicic acid Machine acid HCl dealumination (DA8), though allowing mesopore volume increased, B acid/L acid ratio is not so good as molecular sieve provided by the invention It is high.The present invention uses compound acid system, under three kinds of sour synergistic effects, can ensure crystal structure of molecular sieve and mesoporous hole Molecular sieve silica alumina ratio is effectively improved on the premise of road structural intergrity, adjusts aluminium distribution, improves acid distribution, molecular sieve surface is rich Silicon can inhibit the generation of the non-selective side reaction in surface, mesoporous abundant, be conducive to the progress of residual oil cracking reaction.
The following examples illustrate catalyst provided by the invention and preparation method thereof, the wherein property of raw materials such as Under：Kaolin (Suzhou China Kaolin Co., Ltd, 75 weight % of solid content), (Shandong catalyst branch company, aluminium oxide contain Aluminum sol Measure as 22.5 weight %).
Embodiment 1-6
Kaolin is configured to slurries of the solid content for 30 weight % with decationized Y sieve water, is stirred evenly, will with hydrochloric acid Slurries pH is adjusted to 2.5, keeps the pH value, stood at 50 DEG C aging 1 it is small when after add Aluminum sol, stirring 1 forms colloid when small, The Y molecular sieve prepared prepared by embodiment is added, adds or be added without water, forming catalyst slurry, (solid content is 35 weights Measure %).Microspherical catalyst is made in spray drying after continuing stirring.Then by microspherical catalyst when 500 DEG C of roastings 1 are small, then At 60 DEG C (wherein, ammonium sulfate is washed with ammonium sulfate：Microspherical catalyst：Water=0.5:1:10) it is less than 0.25 weight to sodium oxide content % is measured, is then eluted and is filtered with deionized water, dried afterwards at 110 DEG C, obtain catalyst CA-CF, specific catalyst Proportioning in terms of butt is shown in Table 4.
Comparative example 1-10
Method according to embodiment 1-6 prepares catalytic cracking catalyst, unlike, by the Y molecular sieve in embodiment 1-6 Replace with and prepare Y molecular sieve DB1-DB2 and DA1-DA8 prepared by comparative example, obtain catalyst CDB1-CDB2 and CDA1-CDA8, Specific proportioning of the catalyst in terms of butt is shown in Table 4.
Testing example
By the catalytic cracking catalyst CA-CF of above-mentioned preparation, aging 12 is small under 800 DEG C, 100% steam atmosphere respectively When, it is filled in afterwards in small fixed flowing bed ACE devices, loadings are each 9g.Then, reaction temperature for 530 DEG C, Air speed is 16h-1, agent weight of oil ratio be 5:Catalytic cracking reaction, reaction result are carried out to the feedstock oil shown in table 3 under conditions of 1 As shown in table 5.
Test comparison example
Catalytic cracking reaction is carried out to feedstock oil according to the method for testing example, the difference is that catalyst CA-CF is divided Not Yong the catalytic cracking catalyst CDB1-CDB2 and CDA1-CDA8 of identical weight part substitute, reaction result is as shown in table 5.
Table 5 the result shows that, the excellent heavy oil conversion performance of the catalyst for preparing of the present invention, the gasoline and liquefied gas of higher are received Rate, lower coke yield.
Table 1
Molecular sieve A DB1 DB2 B C D E F
P2O5/ (w%) 5.0 0 0 3.2 6.1 8.7 1.5 5.7
RE2O3/ (w%) 5.2 0 4.1 18.2 16.4 11.5 7.8 18.6
Cell parameter/angstrom 24.48 24.44 24.49 24.50 24.43 24.40 24.42 24.44
VIt is mesoporous/VTotal hole, % 33 19 35 36 58 62 31 60
(strong acid acid amount/total acid content)/% 48 42 43 58 51 26 42 55
The sour amount of B acid/L acid acid amounts 50 41 34 89 84 79 63 92
S1/S2 2.7 3.1 2.7 2.6 2.9 3.3 3.8 2.2
S3/ S, % 4.7 3.0 4.8 4.8 3.8 3.2 3.0 3.8
D (Al distributions) 0.80 0.53 0.88 0.89 0.71 0.51 0.50 0.63
In form：
S1For27Chemical shift is the peak area of 60ppm ± 2ppm resonance signals in Al MAS H NMR spectroscopies；
S2For27Chemical shift is the peak area of 55ppm ± 2ppm resonance signals in Al MAS H NMR spectroscopies；
S3For27Chemical shift is the peak area of 0ppm ± 2ppm resonance signals in Al MAS H NMR spectroscopies；
S is27The sum of peak area of above three characteristic peak in Al MAS H NMR spectroscopies.
Table 2
Table 3
Project Feedstock oil
Density (20 DEG C), g/cm3 0.9334
Refractive power (70 DEG C) 1.5061
Four components, m%
Saturated hydrocarbons 55.6
Aromatic hydrocarbons 30
Colloid 14.4
Asphalitine <0.1
Solidification point, DEG C 34
Tenor, ppm
Ca 3.9
Fe 1.1
Mg <0.1
Na 0.9
Ni 3.1
Pb <0.1
V 0.5
C m% 86.88
H m% 11.94
S m% 0.7
Carbon residue m% 1.77
Table 4
Table 5

Claims (18)

1. a kind of catalytic cracking catalyst, with dry basis, the catalyst contains the phosphorous and rare earth of 25-75 weight % The natural mineral matter of Y molecular sieve, the inorganic oxide binder of 10-30 weight % and 15-65 weight %；Wherein, it is described phosphorous Cell parameter with the Y molecular sieve of rare earth is 24.35-24.55 angstroms；With P2O5Count and on the basis of the butt weight of molecular sieve, institute The phosphorus content for stating molecular sieve is 0.3-10 weights %；With RE2O3Count and on the basis of the butt weight of molecular sieve, the molecular sieve Content of rare earth is 0.5-19 weights %；The Al distributed constants D of the molecular sieve meets：0.4≤D≤0.9, wherein, D=Al (S)/Al (C), Al (S) represents the inside H in crystal face edge using the zeolite crystal of TEM-EDS methods measure apart from interior any more than 100 The aluminium content in square nanometers region, Al (C) are represented using in the geometry of crystal face described in the zeolite crystal of TEM-EDS methods measure The outside H of the heart is somebody's turn to do apart from interior any aluminium content for being more than 100 square nanometers regions wherein the H arrives for the crystal face edge point The 10% of crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25-65%；The molecule The ratio that the sour amount of the strong acid of sieve accounts for total acid content is 20-60%, and the ratio between B acid acid amounts and L acid acid amounts are 20-100；The molecular sieve 's27In Al MAS H NMR spectroscopies, chemical shift be the peak area of 60ppm ± 2ppm resonance signals and chemical shift be 55ppm ± The ratio between peak area of 2ppm resonance signals is (1.5-5)：1, chemical shift accounts for Zong Feng faces for the peak area of 0 ± 2ppm resonance signals Long-pending ratio is not more than 5%.
2. catalytic cracking catalyst according to claim 1, wherein, the cell parameter of the molecular sieve is 24.40- 24.52 angstroms；With P2O5Count and on the basis of the butt weight of molecular sieve, the phosphorus content of the molecular sieve is 1-8 weights %；With RE2O3 Count and on the basis of the butt weight of molecular sieve, the content of rare earth of the molecular sieve is 3-16 weights %；The Al of the molecular sieve points Cloth parameter D meets：0.55≤D≤0.8；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30-61%；Described point The ratio that the sour amount of strong acid of son sieve accounts for total acid content is 25-55%, and the ratio between B acid acid amounts and L acid acid amounts are 35-75；The molecular sieve 's27In Al MAS H NMR spectroscopies, chemical shift be the peak area of 60ppm ± 2ppm resonance signals and chemical shift be 55ppm ± The ratio between peak area of 2ppm resonance signals is (2-4)：1, chemical shift accounts for total peak area for the peak area of 0 ± 2ppm resonance signals Ratio be not more than 3%.
3. catalytic cracking catalyst according to claim 1, wherein, the rare earth be in lanthanum, cerium, praseodymium and neodymium extremely Few one kind.
4. catalytic cracking catalyst according to claim 1, wherein, the natural mineral matter include selected from kaolin, In halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite at least One kind, the inorganic oxide binder are included in silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina It is at least one.
5. a kind of preparation method of catalytic cracking catalyst, the preparation method include：Catalytic cracking catalyst will be used to prepare It is beaten and is spray-dried after raw material and water mixing；Wherein,
With dry basis, the raw material includes the Y molecular sieve of the phosphorous and rare earth of 25-75 weight %, the nothing of 10-30 weight % The precursor of machine adhesive oxides and the natural mineral matter of 15-65 weight %；
The described phosphorous and cell parameter of the Y molecular sieve of rare earth is 24.35-24.55 angstroms；With P2O5Count and with the butt of molecular sieve On the basis of weight, the phosphorus content of the molecular sieve is 0.3-10 weights %；With RE2O3Count and on the basis of the butt weight of molecular sieve, The content of rare earth of the molecular sieve is 0.5-19 weights %；The Al distributed constants D of the molecular sieve meets：0.4≤D≤0.9, its In, D=Al (S)/Al (C), Al (S) represent the inside H distances in crystal face edge of the zeolite crystal using TEM-EDS methods measure Interior any aluminium content for being more than 100 square nanometers regions, Al (C) represent the zeolite crystal institute using TEM-EDS methods measure The outside H of geometric center of crystal face is stated apart from interior any aluminium content for being more than 100 square nanometers regions, wherein the H is the crystalline substance Face edge point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25-65%；The ratio that the sour amount of the strong acid of the molecular sieve accounts for total acid content is 20-60%, and the ratio between B acid acid amounts and L acid acid amounts are 20- 100；The molecular sieve27In Al MAS H NMR spectroscopies, chemical shift is the peak area and chemical potential of 60ppm ± 2ppm resonance signals It is (1.5-5) to move as the ratio between peak area of 55ppm ± 2ppm resonance signals：1, chemical shift is the peak of 0 ± 2ppm resonance signals The ratio that area accounts for total peak area is not more than 5%.
6. preparation method according to claim 5, wherein, the described phosphorous and Y molecular sieve of rare earth preparation process includes：
A, NaY molecular sieve is subjected to ammonium exchange processing, and after being filtered and being washed, obtains ammonium and exchange molecular sieve；Wherein, with oxygen Change sodium meter and on the basis of the butt weight that the ammonium exchanges molecular sieve, the sodium oxide content that the ammonium exchanges molecular sieve is less than 5 Weight %；
B, gained ammonium in step a is exchanged into molecular sieve and carries out calcination process, obtain roasting molecular sieve；
C, gained roasting molecular sieve in step b is subjected to dealumination complement silicon processing using silicon tetrachloride gas in anhydrous conditions, obtained To dealumination complement silicon molecular sieve；
D, gained dealumination complement silicon molecular sieve in step c is subjected to the first dealuminzation in the acid solution being made of organic acid and inorganic acid Processing, and after being filtered and being washed, obtain the first dealuminzation molecular sieve；
E, the first dealuminzation molecular sieve of gained in step d is subjected to alkali process in inorganic alkali solution, and after being filtered and being washed, Obtain alkali process molecular sieve；
F, it is gained alkali process molecular sieve in step e is molten in the Compound-acid dealumination agent being made of fluosilicic acid, organic acid and inorganic acid The second dealumination treatment is carried out in liquid, and after being filtered and being washed, obtains the second dealuminzation molecular sieve；
G, by step f gained the second dealuminzation molecular sieve in the dipping solution containing phosphorus-containing compound and compounds containing rare earth into Row impregnation, and filtered, washed and in steam atmosphere after progress hydrothermal calcine processing, obtain described phosphorous and dilute The Y molecular sieve of soil.
7. preparation method according to claim 6, wherein, the condition of calcination process includes described in step b：Calcination atmosphere For air atmosphere, temperature is 300-600 DEG C, when the time is 0.5-4 small.
8. preparation method according to claim 6, wherein, the condition of the processing of dealumination complement silicon described in step c includes：Temperature For 200-600 DEG C, when the time is 0.5-4 small.
9. preparation method according to claim 6, wherein, organic acid described in acid solution described in step d is selected from second At least one of ethylenediamine tetraacetic acid (EDTA), oxalic acid, citric acid and sulfosalicylic acid, inorganic acid are in hydrochloric acid, sulfuric acid and nitric acid At least one.
10. preparation method according to claim 6, wherein, the condition of the first dealumination treatment includes described in step d：With The weight ratio of the molecular sieve of dry basis, organic acid and inorganic acid is 1：(0.03-0.3):(0.02-0.4)；First dealuminzation Treatment temperature is 25-100 DEG C, when the first dealumination treatment time was 0.5-6 small.
11. preparation method according to claim 6, wherein, inorganic alkali solution described in step e is molten selected from sodium hydroxide At least one of liquid, potassium hydroxide solution, lithium hydroxide solution and ammonium hydroxide.
12. preparation method according to claim 6, wherein, the condition of alkali process includes described in step e：With dry basis The molecular sieve of gauge and the weight ratio of inorganic base are 1：(0.02-0.6)；Its alkali purification temp is 25-100 DEG C, the alkali process time For 0.5-6 it is small when.
13. preparation method according to claim 6, wherein, organic acid is described in Compound-acid dealumination agent described in step f Selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, inorganic acid be selected from hydrochloric acid, sulfuric acid and At least one of nitric acid.
14. preparation method according to claim 6, wherein, the condition of the second dealumination treatment includes described in step f：With The molecular sieve of dry basis, fluosilicic acid, the weight ratio of organic acid and inorganic acid are 1：(0.03-0.3):(0.05-0.3): (0.05-0.25)；Second dealumination treatment temperature is 25-100 DEG C, when the second dealumination treatment time was 0.5-6 small.
15. preparation method according to claim 6, wherein, phosphorus-containing compound described in step g is selected from phosphoric acid, phosphoric acid At least one of hydrogen ammonium, ammonium dihydrogen phosphate and ammonium phosphate, the compounds containing rare earth are in containing lanthanum, cerium, praseodymium and neodymium At least one chlorate and/or nitrate.
16. preparation method according to claim 6, wherein, the condition of impregnation includes described in step g：With P2O5Meter Phosphorus-containing compound, with RE2O3Compounds containing rare earth of meter and using the weight ratio of the molecular sieve of dry basis as (0.001- 0.1)：(0.11-0.32)：1, the dipping solution with using the weight ratio of the molecular sieve of dry basis as (6-25)：1；It is described The temperature of impregnation is 30-90 DEG C, when the time of impregnation is 0.5-3 small.
17. preparation method according to claim 6, wherein, the condition of the processing of hydrothermal calcine described in step g includes：Temperature Spend for 450-750 DEG C, when the time is 0.5-6 small, steam atmosphere is the steam atmosphere of 100 body %.
18. preparation method according to claim 5, wherein, the natural mineral matter includes high selected from kaolin, more water At least one of ridge soil, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, The precursor of the inorganic oxide binder includes selected from Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and contains At least one of phosphorus Aluminum sol.
CN201610921147.3A 2016-10-21 2016-10-21 A kind of catalytic cracking catalyst and preparation method thereof Active CN107970971B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610921147.3A CN107970971B (en) 2016-10-21 2016-10-21 A kind of catalytic cracking catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610921147.3A CN107970971B (en) 2016-10-21 2016-10-21 A kind of catalytic cracking catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107970971A true CN107970971A (en) 2018-05-01
CN107970971B CN107970971B (en) 2019-11-15

Family

ID=62004511

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610921147.3A Active CN107970971B (en) 2016-10-21 2016-10-21 A kind of catalytic cracking catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107970971B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111744534A (en) * 2019-03-27 2020-10-09 中国石油化工股份有限公司 Preparation method of hierarchical pore composite material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323739A (en) * 2000-05-12 2001-11-28 中国石油化工集团公司 Y-type molecular sieve and its prepn.
CN102020289A (en) * 2009-09-10 2011-04-20 中国石油化工股份有限公司 Super-stable Y zeolite, preparation method and application thereof
CN102264643A (en) * 2008-12-22 2011-11-30 道达尔炼油与销售部 Modified y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof
CN105148985A (en) * 2014-06-10 2015-12-16 中国石油化工股份有限公司 Catalytic cracking catalyst, preparation method thereof and application
CN105268469A (en) * 2014-06-10 2016-01-27 中国石油化工股份有限公司 Catalytic cracking catalyst, and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323739A (en) * 2000-05-12 2001-11-28 中国石油化工集团公司 Y-type molecular sieve and its prepn.
CN102264643A (en) * 2008-12-22 2011-11-30 道达尔炼油与销售部 Modified y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof
CN102020289A (en) * 2009-09-10 2011-04-20 中国石油化工股份有限公司 Super-stable Y zeolite, preparation method and application thereof
CN105148985A (en) * 2014-06-10 2015-12-16 中国石油化工股份有限公司 Catalytic cracking catalyst, preparation method thereof and application
CN105268469A (en) * 2014-06-10 2016-01-27 中国石油化工股份有限公司 Catalytic cracking catalyst, and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111744534A (en) * 2019-03-27 2020-10-09 中国石油化工股份有限公司 Preparation method of hierarchical pore composite material

Also Published As

Publication number Publication date
CN107970971B (en) 2019-11-15

Similar Documents

Publication Publication Date Title
CN107973314B (en) A kind of phosphorous and rare earth Y molecular sieve and preparation method thereof
CN107970974B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107970999B (en) A kind of assistant for calalytic cracking and preparation method thereof containing phosphorous Beta molecular sieve
CN107973315B (en) A kind of phosphorous and rare earth Y molecular sieve and preparation method thereof
CN107971003A (en) It is a kind of to contain phosphorous and assistant for calalytic cracking of Beta molecular sieves of carried metal and preparation method thereof
CN108452832A (en) A kind of phosphorous and rare earth modified Y type molecular sieve and preparation method thereof rich in second hole
CN107973312B (en) It is a kind of rich in mesoporous Y molecular sieve and preparation method thereof
CN107970975B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107970970B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107970973B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107971000A (en) A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof
CN107970971B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107970978A (en) MFI structure molecular sieve a kind of phosphorous and containing carried metal and preparation method thereof
CN107973308A (en) A kind of phosphorous MFI structure molecular sieve and preparation method thereof
CN107973311B (en) A kind of Y molecular sieve and preparation method thereof
CN107970972B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107973313A (en) It is a kind of to be rich in mesoporous Y molecular sieve and preparation method thereof
CN107971031B (en) A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket
CN107970976B (en) A kind of catalytic cracking catalyst and preparation method thereof
CN107971027A (en) A kind of aromatisation auxiliary agent and preparation method thereof
CN107974274A (en) MFI structure molecular sieve a kind of phosphorous and containing carried metal and preparation method thereof
CN107970984A (en) A kind of assistant for calalytic cracking for improving octane number bucket and preparation method thereof
CN107973310B (en) A kind of Y molecular sieve and preparation method thereof containing rare earth
CN107970969A (en) A kind of Y molecular sieve containing rare earth and preparation method thereof
CN106745046B (en) Catalytic cracking catalyst of the molecular sieve containing Y and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant