CN107970970B - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents

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

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CN107970970B
CN107970970B CN201610921140.1A CN201610921140A CN107970970B CN 107970970 B CN107970970 B CN 107970970B CN 201610921140 A CN201610921140 A CN 201610921140A CN 107970970 B CN107970970 B CN 107970970B
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molecular sieve
acid
weight
peak area
ratio
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CN107970970A (en
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罗一斌
朱玉霞
欧阳颖
陈振宇
庄立
任飞
刘建强
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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    • 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
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (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 rich in mesoporous Y molecular sieve, the inorganic oxide binder of 10-30 weight % and 15-65 weight % of 25-75 weight %；Wherein, the cell parameter rich in mesoporous Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >=90%；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8；The micropore specific area of the molecular sieve is 650-800 meters2/ gram；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-65%；Chemical shift is the peak area of 60ppm ± 2ppm resonance signal and chemical shift be the ratio between peak area of 55ppm ± 2ppm resonance signal is (1.5-5): 1, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the ratio of total peak area no more than 5%.With excellent heavy oil conversion performance, higher gasoline and yield of liquefied gas when catalytic cracking catalyst provided by the invention is 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 catalysts and preparation method thereof.
Background technique
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, in this process it is generally necessary to using having high cracking activity Catalysis material.Molecular sieve is due to being widely used in petroleum refining with Shape-selective, higher specific surface and stronger acidity In system and processing industry.Y type molecular sieve (HY, REY, USY) has just been always that catalysis is split since the sixties in last century of use for the first time Change, the chief active constituent element of hydrocracking catalyst.However, the polycyclic compound with the aggravation of crude oil heaviness, in raw material Content dramatically increases, and the Y type molecular sieve aperture as predominant cracking group member only has 0.74nm, evaporates 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 ring alkane) 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, influences 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 is mainly comprised the processes of using commercially available USY as raw material, in the atmosphere of 100% vapor, is handled for 24 hours 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%.
It is original with HY or USY in the method for the Y type molecular sieve of the disclosed preparation containing mesopore of United States Patent (USP) US 5601798 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 specific 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, the alkali process 0.1~for 24 hours 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 carries out ammonium exchange, dealumination complement silicon processing, obtained Y type point to the molecular sieve after alkali process 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, handles followed by aqueous solutions of organic acids, is carrying out NaOH processing to the molecular sieve after acid processing, It is finally handled using aqueous ammonium nitrate solution, obtains the Y type molecular sieve of containing mesopore.Obtained Y type molecular sieve, it is rich in micro- Hole, mesoporous pore volume can arrive 0.5mL/g~1.5mL/g.
Chinese patent CN104760973 discloses a kind of Y type molecular sieve and preparation method thereof of mesoporous content of superelevation, 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 the dry gas being saturated by dealumination complement silicon in the y-type zeolite of processing, reacts 0.5~7h, obtains crude product；Or anhydrous dry Under dry environment, while temperature to be at the uniform velocity warming up to 250~700 DEG C, mended to by being passed through in pretreated y-type zeolite by dealuminzation The dry gas of silicon saturation, reacts 0.5~7h, obtains crude product；Crude product carries out sour processing；To acid treated crude product 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 lower.
Summary 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, higher gasoline and yield of liquefied gas when catalyst is for heavy oil catalytic cracking.
To achieve the goals above, the present invention provides a kind of catalytic cracking catalyst, with dry basis, the catalyst Mesoporous Y molecular sieve, the inorganic oxide binder of 10-30 weight % and 15-65 weight % are rich in containing 25-75 weight % Natural mineral matter；Wherein, the cell parameter rich in mesoporous Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >= 90%；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) expression are adopted The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS method is apart from interior any aluminium for being greater than 100 square nanometers regions Content, Al (C) indicate that the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is interior and appoint Meaning is greater than the aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The micropore specific area of the molecular sieve is 650-800 meters2/ gram；The mesopore volume of the molecular sieve accounts for total pore volume Ratio be 20-65%；The molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is the peak of 60ppm ± 2ppm resonance signal Area and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signal is (1.5-5): 1, chemical shift is 0 ± 2ppm The peak area of resonance signal accounts for the ratio of total peak area no more than 5%.
Preferably, the cell parameter of the molecular sieve is 24.40-24.52 angstroms, relative crystallinity >=95%；The molecule The Al distribution parameter D of sieve meets: 0.35≤D≤0.75；The micropore specific area of the molecular sieve is 680-750 meters2/ gram；Institute It is 25-60% that the mesopore volume for stating molecular sieve, which accounts for the ratio of total pore volume,；The molecular sieve27In Al MAS H NMR spectroscopy, chemistry Displacement be that peak area and the chemical shift of 60ppm ± 2ppm resonance signal are the ratio between the peak area of 55ppm ± 2ppm resonance signal For (2-4): 1, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the ratio of total peak area no more than 3%.
Preferably, the natural mineral matter includes being selected from kaolin, halloysite, montmorillonite, diatomite, concave convex 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: that will be used to prepare to urge It is beaten and is spray-dried after raw material and the water mixing of fluidized cracking catalysts；Wherein, with dry basis, the raw material includes 25-75 weight %'s is heavy rich in mesoporous Y molecular sieve, the precursor of the inorganic oxide binder of 10-30 weight % and 15-65 Measure the natural mineral matter of %；The cell parameter rich in mesoporous Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >= 90%；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) expression are adopted The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS method is apart from interior any aluminium for being greater than 100 square nanometers regions Content, Al (C) indicate that the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is interior and appoint Meaning is greater than the aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The micropore specific area of the molecular sieve is 650-800 meters2/ gram；The mesopore volume of the molecular sieve accounts for total pore volume Ratio be 20-65%；The molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is the peak of 60ppm ± 2ppm resonance signal Area and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signal is (1.5-5): 1, chemical shift is 0 ± 2ppm The peak area of resonance signal accounts for the ratio of total peak area no more than 5%.
Preferably, the preparation step rich in mesoporous Y molecular sieve include: a, will NaY molecular sieve carry out ammonium exchange at Reason, and after being filtered and washed, obtain ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with ammonium exchange molecular sieve On the basis of dry weight, the sodium oxide content % heavy less than 5 of the ammonium exchange molecular sieve；B, by gained ammonium exchange point in step a Son sieve carries out calcination process, obtains roasting molecular sieve；C, gained roasting molecular sieve in step b is used into tetrachloro in anhydrous conditions SiClx gas carries out dealumination complement silicon processing, obtains dealumination complement silicon molecular sieve；D, by step c gained dealumination complement silicon molecular sieve by The first dealumination treatment is carried out in the acid solution of organic acid and inorganic acid composition, and after being filtered and washed, obtains the first dealuminzation Molecular sieve；E, the first dealuminzation molecular sieve of gained in step d is subjected in inorganic alkali solution alkali process, and be filtered and washed Afterwards, alkali process molecular sieve is obtained；F, gained alkali process molecular sieve in step e is formed by fluosilicic acid, organic acid and inorganic acid Compound-acid dealuminzation agent solution in carry out the second dealumination treatment, and after being filtered and washed, obtain described rich in mesoporous Y points Son sieve.
Preferably, it is air atmosphere, temperature 300-600 that the condition of calcination process described in step b, which includes: calcination atmosphere, DEG C, the time is 0.5-4 hours.
Preferably, it is 200-600 DEG C that the condition of the processing of dealumination complement silicon described in step c, which includes: temperature, 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 described in step d includes: 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- The aluminium processing time is 0.5-6 hours.
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 described in step e includes: the weight with the molecular sieve of dry basis and inorganic base The ratio between be 1:(0.02-0.6)；Alkali purification temp is 25-100 DEG C, and the alkali process time is 0.5-6 hours.
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 described in step f include: 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 Degree is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
Preferably, the condition of the second dealumination treatment described in step f include: with the molecular sieve of dry basis, fluosilicic acid, The weight ratio of organic acid and inorganic acid is 1:(0.035-0.2): (0.06-0.2): (0.1-0.2).
Preferably, the natural mineral matter includes being selected from kaolin, halloysite, montmorillonite, diatomite, concave convex rod At least one of stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite, the predecessor of the inorganic oxide binder Object includes selected from least one of silica solution, 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 for heavy oil catalytic cracking, more High gasoline and yield of liquefied gas.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalytic cracking catalyst, and with dry basis, the catalyst contains 25-75 weight %'s Natural mineral matter rich in mesoporous Y molecular sieve, the inorganic oxide binder of 10-30 weight % and 15-65 weight %, preferably The natural minerals of Y molecular sieve containing 30-70 weight %, the inorganic oxide binder of 12-28 weight % and 20-55 weight % Matter；Wherein, the cell parameter rich in mesoporous Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >=90%；It is described The Al distribution parameter D of molecular sieve meets: 0.3≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) indicate to use TEM-EDS The inside H in crystal face edge of the zeolite crystal of method measurement is apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) indicate that the outside H of geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is arbitrarily greater than apart from interior The aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The micropore specific area of the molecular sieve is 650-800 meters2/ gram；The mesopore volume of the molecular sieve accounts for total pore volume Ratio is 20-65%；The molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is the peak face of 60ppm ± 2ppm resonance signal Long-pending and chemical shift is that the ratio between peak area of 55ppm ± 2ppm resonance signal is (1.5-5): 1, chemical shift is that 0 ± 2ppm is total The peak area of vibration signal accounts for the ratio of total peak area no more than 5%.Preferably, the cell parameter of the molecular sieve is 24.40- 24.52 angstroms, relative crystallinity >=95%；The Al distribution parameter D of the molecular sieve meets: 0.35≤D≤0.75；The molecular sieve Micropore specific area be 680-750 meters2/ gram；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25-60%； The molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is the peak area of 60ppm ± 2ppm resonance signal and chemical shift is The ratio between peak area of 55ppm ± 2ppm resonance signal is (2-4): 1, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for The ratio of total peak area is not more than 3%.
According to the present invention, using TEM-EDS method measurement molecular sieve aluminium content be it is well-known to those skilled in the art, Wherein the 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 It states, 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 micropore specific area of the molecular sieve, mesopore volume account for the ratio of total pore volume using nitrogen The method of adsorption desorption measures, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；It is described opposite Crystallinity is the ratio between crystallinity and crystallinity of standard sample of the molecular sieve, and the relative crystallinity uses RIPP146-90 Standard method is measured, and the standard sample is the NaY molecular sieve that Shandong is catalyzed company's production, SiO2/Al2O3For 4.8- 5.0, crystallinity 84.1%；The molecular sieve27The peak area of resonance signal is carried out using integration method in Al MAS H NMR spectroscopy It calculates, is determined before being calculated using integration method using swarming fitting process27Each peak of resonance signal in Al MAS H NMR spectroscopy.
According to the present invention, natural mineral matter refers under the comprehensive function of the various substances of the earth's crust and (claims geologic process) formation Natural simple substance or compound, and distinctive chemical component and relatively-stationary chemical component with chemical formula expression, such as can To include selected from kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, galapectite, hydrotalcite, swelling At least one of soil and rectorite, inorganic oxide binder refer to the inorganic oxide for playing bonding each component in the catalyst Object, such as may 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: that will be used to prepare to urge It is beaten and is spray-dried after raw material and the water mixing of fluidized cracking catalysts；Wherein, with dry basis, the raw material includes 25-75 weight %'s is heavy rich in mesoporous Y molecular sieve, the precursor of the inorganic oxide binder of 10-30 weight % and 15-65 Measure the natural mineral matter of %；The cell parameter rich in mesoporous Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >= 90%；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8, wherein D=Al (S)/Al (C), Al (S) expression are adopted The inside H in crystal face edge of the zeolite crystal measured with TEM-EDS method is apart from interior any aluminium for being greater than 100 square nanometers regions Content, Al (C) indicate that the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method is interior and appoint Meaning is greater than the aluminium content in 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometric center distance 10%；The micropore specific area of the molecular sieve is 650-800 meters2/ gram；The mesopore volume of the molecular sieve accounts for total pore volume Ratio be 20-65%；The molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is the peak of 60ppm ± 2ppm resonance signal Area and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signal is (1.5-5): 1, chemical shift is 0 ± 2ppm The peak area of resonance signal accounts for the ratio of total peak area no more than 5%.
According to the present invention, the preparation step rich in mesoporous Y molecular sieve may include: a, carry out NaY molecular sieve Ammonium exchange processing, and after being filtered and washed, obtain ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena and with ammonium exchange On the basis of the dry weight of molecular sieve, the sodium oxide content % heavy less than 5 of the ammonium exchange molecular sieve；B, by gained in step a Ammonium exchanges molecular sieve and carries out calcination process, obtains roasting molecular sieve；C, in anhydrous conditions by gained roasting molecular sieve in step b Dealumination complement silicon processing is carried out using silicon tetrachloride gas, obtains dealumination complement silicon molecular sieve；D, by gained dealumination complement silicon point in step c Son sieve carries out the first dealumination treatment in the acid solution being made of organic acid and inorganic acid, and after being filtered and washed, obtains First dealuminzation molecular sieve；E, the first dealuminzation molecular sieve of gained in step d is subjected in inorganic alkali solution alkali process, and carried out After filter and washing, alkali process molecular sieve is obtained；F, by gained alkali process molecular sieve in step e by fluosilicic acid, organic acid and nothing The second dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of machine acid composition, and after being filtered and washed, obtains described be rich in Mesoporous Y molecular sieve.
According to the present invention, ammonium exchange processing is well-known to those skilled in the art, for example, NaY molecular sieve can be pressed According to molecular sieve: ammonium salt: water=1:(0.1-1): the weight ratio of (5-10) is filtered in room temperature to after exchanging 0.5-2 hours 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 described in step b can To include: calcination atmosphere as air atmosphere, temperature is 300-600 DEG C, and preferably 400-550 DEG C, the time is 0.5-4 hours, excellent It is selected as 1-3.5 hours.
According to the present invention, dealumination complement silicon processing is well-known to those skilled in the art, for using tetrachloro at high temperature The aluminium element in element silicon substitution molecular sieve in SiClx, for example, the condition of the processing of dealumination complement silicon described in step c includes: temperature Degree be 200-600 DEG C, preferably 300-550 DEG C, the time be 0.5-4 hours, preferably 1-3.5 hours, preferably 100% four It is carried out under silicon chloride atmosphere.
According to the present invention, dealumination treatment is well-known to those skilled in the art, and the first dealumination treatment can described in step d With primary or be performed in multiple times, first organic acid can be mixed with the dealumination complement silicon molecular sieve, then by inorganic acid with it is described The mixing of dealumination complement silicon molecular sieve；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 simultaneously.Institute in step d Stating organic acid described in acid solution can be at least one in ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid Kind, preferably citric acid；Inorganic acid can for selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably nitric acid, described the The condition of one dealumination treatment can be with are as follows: with the weight ratio of the molecular sieve of dry basis, organic acid and inorganic acid for 1: (0.03-0.3): (0.02-0.4), preferably 1:(0.05-0.25): (0.05-0.25)；First dealumination treatment temperature is 25- 100 DEG C, the first dealumination treatment time was 0.5-6 hours.
According to the present invention, alkali process can be used for removing the part framework silicon atom of molecular sieve, generate 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, preferably sodium hydroxide solution, the condition of alkali process described in step e may include: with dry basis The weight ratio of molecular sieve and inorganic base is 1:(0.02-0.6), preferably 1:(0.05-0.4)；Alkali purification temp is 25-100 DEG C, the alkali process time is 0.5-6 hours.
According to the present invention, although dealumination treatment be it 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 be primary or be performed in multiple times, can be with Organic acid is mixed with the alkali process molecular sieve first, then mixes fluosilicic acid and inorganic acid with the alkali process molecular sieve, It can be with for first organic acid is added in alkali process molecular sieve, then by fluosilicic acid and inorganic acid, cocurrent be added at a slow speed, or is first added Enter fluosilicic acid and add inorganic acid, preferably cocurrent is added at a slow speed for fluosilicic acid and inorganic acid.Compound-acid dealumination agent described in step f Described in organic acid can be for selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably Oxalic acid, inorganic acid can be for selected from least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid.Second dealumination treatment Condition can be with are as follows: the weight ratio with the molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid is 1:(0.03- 0.3): (0.05-0.3): (0.05-0.25), preferably 1:(0.035-0.2): (0.06-0.2): (0.1-0.2)；Second dealuminzation Treatment temperature is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
It is of the present invention washing be it is well-known to those skilled in the art, refer generally to wash, for example, can 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 for generating in catalytic cracking catalyst The catalytic cracking catalyst of inorganic oxide binder prepares raw material, for example, may 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 instrument commonly used by those skilled in the art and Reagent.
Cell parameter of the present invention is measured using RIPP145-90 standard method, and the measuring method is shown in " Petrochemical Engineering Analysis Method (RIPP test method) ", Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes.
Relative crystallinity of the present invention is measured using RIPP146-90 standard method, and the measuring method is shown in " petroleum Work analysis method (RIPP test method) ", Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes.
Relative crystallinity of the present invention is embodiment crystallinity/standard sample crystallinity.Standard sample used is Shandong catalysis The NaY, SiO of company's production2/Al2O3=4.8-5.0, crystallinity=84.1%.
Research method of the TEM-EDS measuring method of the present invention referring to solid catalyst, petrochemical industry, 29 (3), 2000: 227。
Micropore specific area of the invention, mesoporous pore volume, the measuring method of total pore volume are as follows:
The AS-3 produced using Quantachrome instrument company, the measurement of AS-6 static state n2 absorption apparatus.
Instrument parameter: being placed in sample processing system for sample, is evacuated to 1.33 × 10 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/P0=0.98 adsorbance below is the total pore volume of sample, utilizes BJH formula meter 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 present invention27Al MAS NMR is tested using Bruker Avance III 500MHz Nuclear Magnetic Resonance, is resonated Peak spectrogram uses integration method to calculate each peak area after carrying out swarming fitting.
The calculation method of D value is as follows: choosing a crystal grain 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 value are different), choose respectively any one piece in the inside H distance in the crystal face edge be greater than 100 square nanometers regions with And any one piece in the outside H distance of crystal face geometric center is greater than 100 square nanometers regions, measures aluminium content, as Al (S1) With Al (C1), and D1=Al (S1)/Al (C1) is calculated, chooses different crystal grain respectively and measure 5 times, calculating average value is D.
Prepare embodiment 1
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 2h at 600 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 550 DEG C, reaction time 2h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 3g is added in stirring, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 5g oxalic acid is added in stirring, 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 Washing is dried to obtain 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 (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5；Gained molecular sieve is taken to roast 1h at 600 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 550 DEG C, reaction time 1h；Take gained molecular sieve 100g (butt quality) plus water Be beaten solid content be 10 weight % molecular sieve pulps, be added 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 be 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 (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 2h at 500 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 550 DEG C, reaction time 0.5h；Gained 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, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is dried to obtain sieve sample DB2, the physico-chemical property of sieve sample DB2 is listed in table 1 to neutrality.
Prepare comparative example 3
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 4h at 300 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 200 DEG C, reaction time 4h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 146g fluosilicic acid is added in stirring (concentration 20%) is warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is dried to obtain sieve sample DB3, sieve sample DB3's Physico-chemical property is listed in table 1.
Prepare comparative example 4
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 2h at 400 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 300 DEG C, reaction time 4h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, oxalic acid 12g is added in stirring, so 178g hydrochloric acid (mass fraction 10%) is added afterwards, is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is dried to obtain sieve sample DB4, the physico-chemical property of sieve sample DB4 are listed in table 1.
Prepare comparative example 5
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 3h at 350 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 350 DEG C, reaction time 2h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 15g is added in stirring, 200g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, oxalic acid 29g is added in stirring, rises Temperature to 50 DEG C of constant temperature stir 1h, and filtration washing is dried to obtain sieve sample DB5, and the physico-chemical property of sieve sample DB5 is listed in Table 1.
Prepare comparative example 6
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 3h at 350 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 350 DEG C, reaction time 2h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h are warming up to；It will Filter cake add water be beaten solid content be 20 weight % molecular sieve pulps, 245g hydrochloric acid (mass fraction 10%) is added in stirring, rises Temperature to 50 DEG C of constant temperature stir 1h, and filtration washing is dried to obtain sieve sample DB6, and the physico-chemical property of sieve sample DB6 is listed in Table 1.
Prepare comparative example 7
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 3h at 350 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 350 DEG C, reaction time 2h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h are warming up to；It will Filter cake add water be beaten solid content be 20 weight % molecular sieve pulps, 30g oxalic acid is added in stirring, 100g fluorine is then 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 DB7, sieve sample The physico-chemical property of DB7 is listed in table 1.
Prepare comparative example 8
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 3h at 350 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 350 DEG C, reaction time 2h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 3g is added in stirring, 400g hydrochloric acid (mass fraction is then added 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 %, is added 10.42gNaOH (purity 96%), and 50 DEG C of constant temperature stirring 0.5h are warming up to；It will Filter cake add water be beaten solid content be 20 weight % molecular sieve pulps, 188g hydrochloric acid (mass fraction 10%) is added in stirring, so After 100g fluosilicic acid (concentration 20%) is slowly added dropwise, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing is dried to obtain molecular sieve sample Product DB8, the physico-chemical property of sieve sample DB8 are listed in table 1.
Prepare embodiment 2
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 3h at 550 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 550 DEG C, reaction time 2h；Take gained molecular sieve 100g (butt quality) plus water It is configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g is added in stirring, 200g sulfuric acid (mass fraction is then added 10%) time 30min, is added；30 DEG C of constant temperature stirring 2h 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 %, is added 31.25gKOH (purity 96%), and 70 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 15g ethylenediamine tetraacetic is added in stirring Then 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) is slowly added dropwise in acetic acid, be warming up to 50 DEG C of constant temperature and stir 1h is mixed, filtration washing is dried to obtain sieve sample B, and the physico-chemical property of sieve sample B is listed in table 2.
Prepare embodiment 3
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 2.5h at 450 DEG C.Molecular sieve after taking roasting leads under dried over anhydrous environment Enter SiCl4It is saturated dry gas, reaction temperature is 550 DEG C, reaction time 1.5h；Take gained molecular sieve 100g (butt quality) Add water to be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 25g is added in stirring, 250g nitric acid (quality point is then added Number 10%), time 30min is added；90 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Sample plus water are beaten The molecular sieve pulp that solid content is 10 weight % is obtained, is added 35gNaOH (purity 96%), 80 DEG C of constant temperature stirring 0.5h, mistake are warming up to Filter washing is to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 20g oxalic acid is added in stirring, so After 105g hydrochloric acid (mass fraction 10%) and 49g fluosilicic acid (concentration 20%) is slowly added dropwise, be warming up to 70 DEG C of constant temperature stirring 1h, mistake Filter washing is dried to obtain sieve sample C, and the physico-chemical property of sieve sample C is listed in table 2.
Prepare embodiment 4
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 4h at 350 DEG C.Molecular sieve after taking roasting is passed through under dried over anhydrous environment SiCl4It is saturated dry gas, reaction temperature is 250 DEG C, reaction time 3.5h；Gained 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, 100g sulfuric acid (mass fraction is then added 10%) time 1min, is added；55 DEG C of constant temperature stirring 2h 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 %, is added 41gNaOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, crosses diafiltration It washs to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 30g sulfosalicylic acid is added in stirring, 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 dried to obtain sieve sample D, and the physico-chemical property of sieve sample D is listed in table 2.
Prepare embodiment 5
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 0.5h at 350 DEG C.Molecular sieve after taking roasting leads under dried over anhydrous environment Enter SiCl4It is saturated dry gas, reaction temperature is 250 DEG C, reaction time 0.5h；Take gained molecular sieve 100g (butt quality) Add water to be configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 20g is added in stirring, 220g nitric acid (quality is then added Score 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 Molecular sieve pulp of the solid content for 10 weight % is starched to obtain, addition 23gLiOH is warming up to 400 DEG C of constant temperature stirring 2h, and filtration washing is into Property；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 5g oxalic acid is added in stirring, is then slowly added dropwise 148g sulfuric acid (mass fraction 10%) and 125g fluosilicic acid (concentration 20%), are warming up to 80 DEG C of constant temperature stirring 1h, and filtration washing is dry Dry to obtain sieve sample E, the physico-chemical property of sieve sample E is listed in table 2.
Prepare embodiment 6
By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 24.63 angstroms of cell parameter) and NH4Cl and distilled water are according to 1: 1:10 ratio is mixed with beating uniformly, and ammonium exchanges 1h at 70 DEG C, and by sample filtering, washing, drying, the sodium oxide molybdena for measuring molecular sieve contains Measure % heavy less than 5.Gained molecular sieve is taken to roast 0.5h at 550 DEG C.Molecular sieve after taking roasting leads under dried over anhydrous environment Enter SiCl4It is saturated dry gas, reaction temperature is 600 DEG C, reaction time 0.5h；Take gained molecular sieve 100g (butt quality) Add water to be configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 30g is added in stirring, 200g hydrochloric acid (quality point is then added Number 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 The molecular sieve pulp that solid content is 10 weight % is obtained, 46gKOH is added, is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing is into Property；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 6g ethylenediamine tetra-acetic acid is added in stirring, then delays It is slow that 90g nitric acid (mass fraction 10%) and 90g fluosilicic acid (concentration 20%) is added dropwise, 85 DEG C of constant temperature stirring 4h are warming up to, diafiltration is crossed It washs and is dried to obtain sieve sample F, the physico-chemical property of sieve sample F is listed in table 2.
For the Y molecular sieve after alkali process desiliconization it can be seen from data in table 1, using single organic acid oxalic acid dealuminzation (DB5), compound using single inorganic acid HCl dealumination (DB6) and using organic acid oxalic acid and two kinds of acid of inorganic acid hydrochloric acid (DB4) all effectively the Al in molecular sieve can not be removed, and preferable dealuminzation effect could be obtained after only having used fluosilicic acid Fruit.It is mesoporous relatively fewer when fluosilicic acid dealuminzation is used alone (DB3).The present invention uses compound acid system, in three kinds of sour collaborations Under effect, aluminium distribution can be effectively adjusted under the premise of guaranteeing crystal structure of molecular sieve and mesopore orbit structural intergrity, point Son sieve surface Silicon-rich 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, and wherein the property of raw materials is such as Under: kaolin (Suzhou China Kaolin Co., Ltd, 75 weight % of solid content), (Shandong catalyst branch, aluminium oxide contain Aluminum sol Amount is 22.5 weight %).
Embodiment 1-6
Kaolin is configured to the slurries that solid content is 30 weight % with decationized Y sieve water, is stirred evenly, it will with hydrochloric acid Slurries pH is adjusted to 2.5, keeps the pH value, and Aluminum sol is added after standing aging 1 hour at 50 DEG C, stirs 1 hour formation colloid, Y molecular sieve prepared by preparation embodiment is added, is added or is added without water, forming catalyst slurry, (solid content is 35 weights Measure %).Microspherical catalyst is made in spray drying after continuing stirring.Then microspherical catalyst is roasted 1 hour at 500 DEG C, then (wherein, ammonium sulfate: microspherical catalyst: water=0.5:1:10) is washed to sodium oxide content less than 0.25 weight with ammonium sulfate at 60 DEG C % is measured, is then eluted and is filtered with deionized water, dried at 110 DEG C later, obtain catalyst CA-CF, specific catalyst Proportion in terms of butt is shown in Table 4.
Comparative example 1-8
Catalytic cracking catalyst is prepared according to the method for embodiment 1-6, unlike, by the Y molecular sieve in embodiment 1-6 The Y molecular sieve DB1-DB8 for replacing with preparation comparative example preparation, obtains catalyst CDB1-CDB8, specific catalyst is in terms of butt Proportion 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 small fixed flowing bed ACE device later, loadings are respectively 9g.Then, reaction temperature be 530 DEG C, Air speed is 16h-1, agent oil weight ratio be 5:1 under conditions of to feedstock oil shown in table 3 carry out catalytic cracking reaction, reaction result 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 by catalyst CA-CF points Not Yong identical weight part catalytic cracking catalyst CDB1-CDB8 substitution, reaction result is as shown in table 5.
Table 5 the result shows that, the excellent heavy oil conversion performance of catalyst prepared by the present invention and higher yield of gasoline.
Table 1
In table:
S1For27Chemical shift is the peak area of 60ppm ± 2ppm resonance signal in Al MAS H NMR spectroscopy；
S2For27Chemical shift is the peak area of 55ppm ± 2ppm resonance signal in Al MAS H NMR spectroscopy；
S3For27Chemical shift is the peak area of 0ppm ± 2ppm resonance signal in Al MAS H NMR spectroscopy；
S is27The sum of the peak area of above three characteristic peak in Al MAS H NMR spectroscopy.
Table 2
Molecular sieve B C D E F
Relative crystallinity/% 91 93 95 90 91
Cell parameter/angstrom 24.48 24.43 24.39 24.35 24.47
Micropore specific area/(m2/g) 691 706 727 671 706
(VIt is mesoporous/VTotal hole)/% 0.38 0.51 0.59 0.32 0.62
S1/S2 2.4 2.7 3.1 3.5 2.6
S3/ S, % 4.6 3.6 3.0 2.8 3.8
D (Al distribution) 0.73 0.65 0.38 0.35 0.67
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
Freezing 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 (15)

1. a kind of catalytic cracking catalyst, with dry basis, the catalyst contains dividing rich in mesoporous Y for 25-75 weight % The natural mineral matter of son sieve, the inorganic oxide binder of 10-30 weight % and 15-65 weight %；Wherein, described rich in mesoporous The cell parameter of Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >=90%；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8, wherein D=Al(S)/Al(C), Al(S) and it indicates to use the crystal face of the zeolite crystal of TEM-EDS method measurement The inside H in edge is apart from interior any aluminium content for being greater than 100 square nanometers regions, Al(C) it indicates using the measurement of TEM-EDS method The outside H of the geometric center of crystal face described in zeolite crystal is apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein institute Stating H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The micropore specific area of the molecular sieve is 650- 800 meters2/ gram；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-65%, it is described it is mesoporous be greater than for aperture 2 receive Molecular sieve pore passage of the rice less than 100 nanometers；The molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is that 60ppm ± 2ppm is total The peak area of vibration signal and chemical shift are that the ratio between peak area of 55ppm ± 2ppm resonance signal is (1.5-5): 1, chemical shift The ratio of total peak area is accounted for no more than 5% for the peak area of 0 ± 2ppm resonance signal.
2. catalytic cracking catalyst according to claim 1, wherein the cell parameter of the molecular sieve is 24.40- 24.52 angstroms, relative crystallinity >=95%；The Al distribution parameter D of the molecular sieve meets: 0.35≤D≤0.75；The molecular sieve Micropore specific area be 680-750 meters2/ gram；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25-60%；Institute State molecular sieve27In Al MAS H NMR spectroscopy, chemical shift is the peak area of 60ppm ± 2ppm resonance signal and chemical shift is The ratio between peak area of 55ppm ± 2ppm resonance signal is (2-4): 1, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for The ratio of total peak area is not more than 3%.
3. catalytic cracking catalyst according to claim 1, wherein the natural mineral matter include selected from kaolin, At least one of galapectite, montmorillonite, diatomite, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite, the nothing Machine adhesive oxides include selected from least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.
4. a kind of preparation method of catalytic cracking catalyst, which includes: that will be used to prepare catalytic cracking catalyst It is beaten and is spray-dried after raw material and water mixing；Wherein,
With dry basis, the raw material includes the inorganic oxygen rich in mesoporous Y molecular sieve, 10-30 weight % of 25-75 weight % The precursor of compound binder and the natural mineral matter of 15-65 weight %；
The cell parameter rich in mesoporous Y molecular sieve is 24.35-24.55 angstroms, relative crystallinity >=90%；The molecular sieve Al distribution parameter D meet: 0.3≤D≤0.8, wherein D=Al(S)/Al(C), Al(S) indicate using TEM-EDS method measure Zeolite crystal the inside H in crystal face edge apart from interior any aluminium content for being greater than 100 square nanometers regions, Al(C) indicate to adopt The outside H of geometric center of crystal face described in the zeolite crystal measured with TEM-EDS method is arbitrarily greater than 100 square nanometers apart from interior The aluminium content in region, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The molecular sieve Micropore specific area be 650-800 meters2/ gram；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 20-65%, institute Giving an account of hole is that aperture is greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The molecular sieve27In Al MAS H NMR spectroscopy, chemistry Displacement be that peak area and the chemical shift of 60ppm ± 2ppm resonance signal are the ratio between the peak area of 55ppm ± 2ppm resonance signal For (1.5-5): 1, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the ratio of total peak area no more than 5%.
5. the preparation method according to claim 4, wherein the preparation step rich in mesoporous Y molecular sieve includes:
A, NaY molecular sieve is subjected to ammonium exchange processing, and after being filtered and washed, obtains ammonium exchange molecular sieve；Wherein, with oxygen Change sodium meter and on the basis of the dry weight of ammonium exchange molecular sieve, the sodium oxide content of ammonium exchange molecular sieve is less than 5 Weight %；
B, gained ammonium exchange molecular sieve in step a is subjected to calcination process, obtains roasting molecular sieve；
C, it uses silicon tetrachloride gas to carry out dealumination complement silicon processing in anhydrous conditions in gained roasting molecular sieve in step b, obtains 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 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 washed, Obtain alkali process molecular sieve；
F, 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 being carried out in liquid, and after being filtered and washed, obtaining described rich in mesoporous Y molecular sieve, inorganic acid is choosing From at least one of hydrochloric acid, sulfuric acid and nitric acid.
6. preparation method according to claim 5, wherein the condition of calcination process described in step b includes: calcination atmosphere For air atmosphere, temperature is 300-600 DEG C, and the time is 0.5-4 hours.
7. preparation method according to claim 5, wherein the condition of the processing of dealumination complement silicon described in step c includes: temperature It is 200-600 DEG C, the time is 0.5-4 hours.
8. preparation method according to claim 5, 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.
9. preparation method according to claim 5, wherein the condition of the first dealumination treatment described in step d includes: with dry The weight ratio of the molecular sieve of base weight meter, organic acid and inorganic acid is 1:(0.03-0.3): (0.02-0.4)；At first dealuminzation Managing temperature is 25-100 DEG C, and the first dealumination treatment time was 0.5-6 hours.
10. preparation method according to claim 5, 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.
11. preparation method according to claim 5, wherein the condition of alkali process described in step e includes: with dry basis The molecular sieve of meter and the weight ratio of inorganic base are 1:(0.02-0.6)；Alkali purification temp is 25-100 DEG C, the alkali process time It is 0.5-6 hours.
12. preparation method according to claim 5, wherein organic acid described in Compound-acid dealumination agent described in step f is 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.
13. preparation method according to claim 5, wherein the condition of the second dealumination treatment described in step f include: with The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.03-0.3): (0.05-0.3): (0.05-0.25)；Second dealumination treatment temperature is 25-100 DEG C, and the second dealumination treatment time was 0.5-6 hours.
14. preparation method according to claim 5, wherein the condition of the second dealumination treatment described in step f include: with The molecular sieve of dry basis, fluosilicic acid, organic acid and inorganic acid weight ratio be 1:(0.035-0.2): (0.06-0.2): (0.1-0.2).
15. the preparation method according to claim 4, wherein the natural mineral matter includes being selected from kaolin, Ai Luo At least one of stone, montmorillonite, diatomite, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite, the inorganic oxygen The precursor of compound binder includes in silica solution, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol At least one.
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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
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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
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