CN107973310B

CN107973310B - A kind of Y molecular sieve and preparation method thereof containing rare earth

Info

Publication number: CN107973310B
Application number: CN201610920231.3A
Authority: CN
Inventors: 刘建强; 庄立; 罗一斌; 欧阳颖; 舒兴田
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2016-10-21
Filing date: 2016-10-21
Publication date: 2019-11-15
Anticipated expiration: 2036-10-21
Also published as: CN107973310A

Abstract

This disclosure relates to a kind of Y molecular sieve and preparation method thereof containing rare earth, the cell parameter of the molecular sieve is 24.35-24.55 angstroms；The content of rare earth of the molecular sieve is 0.5-19 weight %；The Al distribution parameter 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 ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60-90%, and the ratio between B acid acid amount and L acid acid amount are 20-100；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%.Catalyst is prepared as active component using the molecular sieve of the disclosure, with excellent heavy oil conversion performance and higher yield of gasoline when for heavy oil catalytic cracking reaction, there is lower olefin(e) centent and higher isoparaffin content in gasoline.

Description

A kind of Y molecular sieve and preparation method thereof containing rare earth

Technical field

This disclosure relates to a kind of Y molecular sieve and preparation method thereof containing rare earth.

Background technique

Molecular sieve is due to being widely used in catalysis, absorption with Shape-selective, higher specific surface and stronger acidity With separation etc. fields.Y molecular sieve (HY, REY, USY) is since the sixties in last century of use for the first time, just always catalytic cracking (FCC) the chief active constituent element of catalyst.However, the polycyclic compound content with the aggravation of crude oil heaviness, in FCC feedstock It dramatically increases, diffusivity of the FCC feedstock in molecular sieve pore passage is but remarkably decreased.And the Y molecule as predominant cracking group member Mesh size only has 0.74nm, is used to the heavy ends such as process residual oils, and the accessibility of catalyst active center will become wherein institute Major obstacle containing polycyclic compound (such as polycyclic aromatic hydrocarbon, polycyclic ring alkane) cracking.Simultaneously as molecular sieve outer surface acidity Presence so that cannot enter duct heavy oil molecules surface occur without selection react, influence product distribution.

Poromerics aperture is smaller, surface has more polyoxybiontic weakness in order to overcome, surface Silicon-rich and rich in mesoporous The synthesis of catalysis material is increasingly subject to the attention of people.

A kind of preparation side of the Y molecular sieve of containing mesopore is disclosed in United States Patent (USP) US5,069,890 and US5,087,348 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 molecular sieve mesopore volume increases to 0.14mL/g by 0.02mL/g, but crystallinity drops to 70% by 100%, compares table Area is by 683m²/ g is reduced to 456m²/ g, sour density more drop to 6% by 28.9%.

United States Patent (USP) US5 is original with HY or USY in the method for the Y molecular sieves of 601,798 disclosed preparation containing mesopores Material, is placed in autoclave and NH₄NO₃Solution or NH₄NO₃With HNO₃Mixed solution mix, 115 DEG C -250 DEG C at a temperature of 2h-20h is handled, the mesopore volume of obtained Y molecular sieve is up to 0.2mL/g-0.6mL/g, but crystallinity and specific surface area have It is remarkably decreased.

Chinese patent CN101722022 discloses a kind of alkali treatment modifying method of Y molecular sieve, including according to molecular sieve (butt): highly basic: distilled water=(0.1-2): (0.05-2): Y molecular sieve and strong alkali aqueous solution are beaten by the mass ratio of (4-15) It is uniformly mixed, the alkali process 0.1-24h at 0-120 DEG C, obtained molecular sieve has higher N compared with parent Y molecular sieve₂ Adsorbance.

The method that skeleton rich silicon Y molecular sieve is prepared disclosed in Chinese patent CN 101723399, first with lye to NaY points Son sieve carries out desiliconization pretreatment, then carries out ammonium exchange, dealumination complement silicon processing, obtained Y molecular sieve to the molecular sieve after alkali process It is mesoporous to increased.

Chinese patent CN103172082 discloses a kind of preparation method of the Y molecular sieve of containing mesopore, first to sodium form Y points Son 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, most It is handled afterwards using aqueous ammonium nitrate solution, obtains the Y molecular sieve of containing mesopore.Obtained Y molecular sieve, micropore rich in are mesoporous Pore volume can arrive 0.5mL/g-1.5mL/g.

Chinese patent CN104760973 discloses a kind of Y molecular sieve and preparation method thereof of mesoporous content of superelevation, first will Y-type zeolite pre-processes 1-5h at 300-600 DEG C；It is cooled to 200-600 DEG C；In dried over anhydrous environment, to by pre-processing Y-type zeolite in be passed through by dealumination complement silicon be saturated dry gas, react 0.5-7h, obtain crude product；Or in dried over anhydrous ring Under border, while temperature to be at the uniform velocity warming up to 250-700 DEG C, satisfied to by being passed through in pretreated y-type zeolite by dealumination complement silicon The dry gas of sum reacts 0.5-7h, obtains crude product；Crude product carries out sour processing；Alkali is carried out to acid treated crude product Processing, obtains Y molecular sieve.Y molecular sieve made from this method has the mesoporous content of superelevation, but micro pore volume is lower.

Summary of the invention

Purpose of this disclosure is to provide a kind of Y molecular sieve and preparation method thereof containing rare earth is made with the molecular sieve of the disclosure Catalyst is prepared for active component, with excellent heavy oil conversion performance and higher vapour when for heavy oil catalytic cracking reaction Oil yield has lower olefin(e) centent and higher isoparaffin content in gasoline.

To achieve the goals above, the disclosure provides a kind of Y molecular sieve containing rare earth, and the cell parameter of the molecular sieve is 24.35-24.55 angstroms；With RE₂O₃It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 0.5-19 Weight %；The Al distribution parameter D of the molecular sieve meets: 0.4≤D≤0.9, 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 ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 25-65%；The strong acid acid amount Zhan of the molecular sieve is total The ratio of acid amount is 60-90%, and the ratio between B acid acid amount and L acid acid amount are 20-100；The molecular sieve²⁷In Al MAS H NMR spectroscopy, Chemical shift be 60ppm ± 2ppm resonance signal peak area and chemical shift be 55ppm ± 2ppm resonance signal peak area The ratio between be (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%.

Preferably, the cell parameter of the molecular sieve is 24.40-24.52 angstroms；With RE₂O₃It counts and with the dry basis of molecular sieve On the basis of amount, the content of rare earth of the molecular sieve is 3-16 weight %；The Al distribution parameter D of the molecular sieve 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 strong acid acid amount of the molecular sieve accounts for total acid The ratio of amount is 65-85%, and the ratio between B acid acid amount and L acid acid amount are 35-75；The molecular sieve²⁷In Al MAS H NMR spectroscopy, change Displacement study be 60ppm ± 2ppm resonance signal peak area and chemical shift be 55ppm ± 2ppm resonance signal peak area it Than 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 rare earth is selected from least one of lanthanum, cerium, praseodymium and neodymium.

Preferably, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The molecular sieve it is strong Sour amount accounts for the ratio of total acid content using NH₃- TPD method measures, and the acid site of the strong acid is NH₃Desorption temperature is greater than Acid site corresponding to 300 DEG C；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption； The molecular sieve²⁷The peak area of resonance signal is calculated using integration method in Al MAS H NMR spectroscopy.

The disclosure also provides a kind of preparation method of provided Y molecular sieve containing rare earth of the disclosure, the preparation method Include: a, NaY molecular sieve is subjected to ammonium exchange processing, and after being filtered and washed, obtains ammonium exchange molecular sieve；Wherein, with Sodium oxide molybdena 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 heavy %；B, gained ammonium exchange molecular sieve in step a is subjected to calcination process, obtains roasting molecular sieve；C, by gained in step b Roasting molecular sieve uses silicon tetrachloride gas to carry out dealumination complement silicon processing in anhydrous conditions, obtains dealumination complement silicon molecular sieve；d, Gained dealumination complement silicon molecular sieve in step c is subjected to the first dealumination treatment in the acid solution being made of organic acid and inorganic acid, And after being filtered and washed, the first dealuminzation molecular sieve is obtained；E, by the first dealuminzation molecular sieve of gained in step d in inorganic alkali soluble Alkali process is carried out in liquid, and after being filtered and washed, obtains alkali process molecular sieve；F, by gained alkali process molecule in step e Sieve carries out the second dealumination treatment in the Compound-acid dealuminzation agent solution being made of fluosilicic acid, organic acid and inorganic acid, and carries out After filter and washing, the second dealuminzation molecular sieve is obtained；G, the second dealuminzation molecular sieve of gained in step f is being contained into compounds containing rare earth Dipping solution in carry out impregnation, and be filtered, washed and in steam atmosphere carry out hydrothermal calcine processing after, obtain To the Y molecular sieve containing rare earth.

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, compounds containing rare earth described in step g are selected from the chlorination containing at least one of lanthanum, cerium, praseodymium and neodymium Salt and/or nitrate.

Preferably, the condition of impregnation described in step g includes: with RE₂O₃The rare earth of meter and dividing with dry basis Son sieve weight ratio be (0.11-0.32): 1, the dipping solution with the weight ratio of the molecular sieve of dry basis be (6- 25): 1；The temperature of the impregnation is 30-90 DEG C, and the time of impregnation is 0.5-3 hours.

Preferably, it is 450-750 DEG C that the condition of the processing of hydrothermal calcine described in step g, which includes: temperature, time 0.5-6 Hour, steam atmosphere is the vapor of 100 volume %.

The disclosure provide by ammonium exchange, roasting, dealumination complement silicon, the first dealuminzation, alkali process and the second dealumination treatment Y molecular sieve containing rare earth, molecular sieve surface Silicon-rich can inhibit the generation of the non-selective side reaction in surface, and mesoporous abundant and rare earth contains Amount is suitable for being conducive to the progress of residual oil cracking reaction, can be improved the conversion capability of heavy oil, while can reduce alkene in gasoline Content and raising isoparaffin content.

Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.

Specific embodiment

The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.

The disclosure provides a kind of Y molecular sieve containing rare earth, and the cell parameter of the molecular sieve is 24.35-24.55 angstroms；With RE₂O₃It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 0.5-19 weight %；The molecular sieve Al distribution parameter D meet: 0.4≤D≤0.9, wherein D=Al (S)/Al (C), Al (S) indicate using TEM-EDS method survey The inside H in crystal face edge of fixed zeolite crystal is indicated apart from interior any aluminium content for being greater than 100 square nanometers regions, Al (C) The outside H of geometric center of crystal face described in zeolite crystal using the measurement of TEM-EDS method arbitrarily receives greater than 100 squares apart from interior The aluminium content in rice region, wherein the H is that the crystal face edge point arrives the 10% of the crystal face geometric center distance；The molecule The ratio that the mesopore volume of sieve accounts for total pore volume is 25-65%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 60- The ratio between 90%, B acid acid amount and L acid acid amount are 20-100；The molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift 60ppm The peak area of ± 2ppm resonance signal and chemical shift are that 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%；Preferably, the molecular sieve Cell parameter be 24.40-24.52 angstroms；With RE₂O₃Count and on the basis of the dry weight of molecular sieve, the rare earth of the molecular sieve Content is 3-16 weight %；The Al distribution parameter D of the molecular sieve meets: 0.55≤D≤0.8；The mesopore volume of the molecular sieve The ratio for accounting 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 65-85%, B acid acid amount With L acid acid amount the ratio between be 35-75；The molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift is 60ppm ± 2ppm resonance letter Number peak area and chemical shift be the ratio between peak area of 55ppm ± 2ppm resonance signal be (2-4): 1, chemical shift for 0 ± The peak area of 2ppm resonance signal accounts for the ratio of total peak area no more than 3%.

According to the disclosure, rare earth is well-known to those skilled in the art, the hydrothermal stability etc. with increase molecular sieve Effect, for example, the rare earth can be for selected from least one of lanthanum, cerium, praseodymium and neodymium.

According to the disclosure, the aluminium content using TEM-EDS method measurement molecular sieve 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 disclosure 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 disclosure, the mesopore volume of the molecular sieve account for the ratio of total pore volume using nitrogen adsorption desorption method into Row measurement, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The strong acid acid amount of the molecular sieve accounts for The ratio of total acid content uses NH₃- TPD method measures, and the acid site of the strong acid is NH₃It is right that desorption temperature is greater than 300 DEG C of institutes The acid site answered；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption；The molecule Sieve²⁷The peak area of resonance signal is calculated using integration method in Al MAS H NMR spectroscopy, before being calculated using integration method It is determined using swarming fitting process²⁷Each peak of resonance signal in Al MAS H NMR spectroscopy.

According to the disclosure, 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 disclosure, 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 disclosure, dealumination complement silicon processing be it is well-known to those skilled in the art, at high temperature use tetrachloro 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 disclosure, dealumination treatment be it is well-known to those skilled in the art, 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 disclosure, 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 disclosure, 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.

According to the disclosure, compounds containing rare earth are well-known to those skilled in the art, for example, containing dilute described in step g Earth compounds can be for selected from chlorate and/or nitrate containing at least one of lanthanum, cerium, praseodymium and neodymium, preferably lanthanum chloride And/or lanthanum nitrate.

According to the disclosure, impregnation be it is well-known to those skilled in the art, for example, impregnation described in step g Condition may include: with RE₂O₃The compounds containing rare earth of meter and with the weight ratio of the molecular sieve of dry basis be (0.11- 0.32): 1, preferably (0.15-0.23): 1, the dipping solution with the weight ratio of the molecular sieve of dry basis be (6- 25): 1, preferably (8-15): 1；The temperature of the dipping is 30-90 DEG C, and preferably 60-85 DEG C, the time of dipping is 0.5-3 Hour, preferably 1-2 hours.

According to the disclosure, hydrothermal calcine processing be it is well-known to those skilled in the art, at hydrothermal calcine described in step g The condition of reason may include: that temperature is 450-750 DEG C, and preferably 550-700 DEG C, the time is 0.5-6 hours, and steam atmosphere is The steam atmosphere of 100 volume %.

Washing described in the disclosure is well-known to those skilled in the art, refers generally to wash, for example, 5-10 times can be used 30-60 DEG C of water of molecular sieve elutes molecular sieve.

The disclosure will be further illustrated by embodiment below, but therefore the disclosure is not any way limited, Instrument and reagent used by the embodiment of the present disclosure, unless otherwise instructed, be instrument commonly used by those skilled in the art and Reagent.

Influence of the molecular sieve in catalytic cracking of petroleum hydrocarbon to heavy oil conversion ratio, gasoline yield, gasoline composition uses heavy oil It is micro- counter to be evaluated.Feedstock oil is to mix slag VGO, and molecular sieve passes through 800 DEG C, 17h, and the processing of 100% vapor hydrothermal aging is evaluated Condition be 500 DEG C of reaction temperature, 600 DEG C of regeneration temperature, oil ratio 5.92.

The cell parameter of the disclosure is measured using RIPP145-90 standard method, and the measuring method is shown in " petrochemical industry point Analysis method (RIPP test method) ", Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes.

Research method of the TEM-EDS measuring method of the disclosure referring to solid catalyst, petrochemical industry, 29 (3), 2000: 227。

The mesoporous pore volume of the disclosure, 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 B acid acid amount of the disclosure and the measuring method of L acid acid amount are as follows:

The FTS3000 type Fourier infrared spectrograph produced using BIO-RAD company, 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 clean, is cooled to room temperature.Pressure is imported into pond in situ is The pyridine steam of 2.67Pa is warming up to 200 DEG C, is evacuated to 10 again after balancing 30min^-3Pa keeps 30min, is cooled to room Temperature, in 1400-1700cm^-1Scanning, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions in wave-number range.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 amount and L acid acid amount.

The total acid content of the disclosure and the measuring method of strong acid acid amount are as follows:

Using II 2920 temperature programmed desorption instrument of Merck & Co., Inc, U.S. Autochem.

Test condition: weighing 0.2g sample to be tested and be packed into sample cell, is placed in conductance cell heating furnace, and He gas is carrier gas (50mL/ Min), 600 DEG C are warming up to the rate 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 mixture (10.02%NH₃+ 89.98%He) absorption 30min, it is further continued for He gas It is steady to baseline to purge 90min, the ammonia of physical absorption is desorbed.600 DEG C are warming up to 10 DEG C/min heating rate 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 are NH₃Desorption temperature be greater than 300 DEG C corresponding to acid site.

The Re of the disclosure₂O₃Content is measured using GB/T 30905-2014 standard method.

The disclosure²⁷Al MAS NMR is 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.

Micro- reactivity of the disclosure is measured using ASTM D5154-2010 standard method.

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.

Embodiment 1

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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 simultaneously, is warming up to 50 DEG C of constant temperature stirring 1h, Filtration washing is to neutrality；By filter cake plus water be beaten the weight of solid content 10 % molecular sieve pulp, it is 60g/L that concentration, which is added, RECl₃Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide₂O₃Account for 36 heavy %, CeO₂Account for 64 heavy %) 120mL, heating 1h is stirred to 60 DEG C of constant temperature, filter cake is roasted 6h in 550 DEG C, 100% water vapour atmosphere, obtains molecular sieve sample by filtration washing Physico-chemical property, heavy oil micro anti-evaluation heavy oil conversion rate, the yield of gasoline of product A, sieve sample A are listed in table 2.

Comparative example 1

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %；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 Physico-chemical property, heavy oil micro anti-evaluation heavy oil conversion rate, the yield of gasoline of DB1 is listed in table 2.

Comparative example 2

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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, 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 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 citric acid is added in stirring, 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 obtains the physico-chemical property of sieve sample DB2, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline composition result to neutrality It is listed in table 2.

Embodiment 2

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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 acetic acid is slowly added dropwise 100g hydrochloric acid (mass fraction 10%) and 15g fluosilicic acid (concentration 20%) simultaneously, is warming up to 50 DEG C of perseverances Temperature stirring 1h, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, be added concentration be The RECl of 160g/L₃Solution 130mL is warming up to 70 DEG C of constant temperature stirring 1.5h, filtration washing, by filter cake in 700 DEG C, 100% water 1h is roasted in steam atmosphere, obtains sieve sample B.The physico-chemical property of sieve sample B, heavy oil micro anti-evaluation heavy oil conversion Rate, gasoline composition result are listed in table 2.

Embodiment 3

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.Gained molecular sieve is taken to roast 2.5h at 450 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 1.5h；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 25g is added in stirring, 250g nitric acid (mass fraction is then added 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 Solid content is the molecular sieve pulp of 10 weight %, is added 35gNaOH (purity 96%), and 80 DEG C of constant temperature stirring 0.5h, filtering are warming up to It washs to neutrality；By filter cake plus water be beaten solid content be 20 weight % molecular sieve pulps, 20g oxalic acid is added in stirring, then 105g hydrochloric acid (mass fraction 10%) and 49g fluosilicic acid (concentration 20%) is slowly added dropwise simultaneously, is warming up to 70 DEG C of constant temperature stirring 1h, Filtration washing is to neutrality；By filter cake plus water be beaten the weight of solid content 15 % molecular sieve pulp, it is 160g/L that concentration, which is added, RECl₃Solution 110mL is warming up to 90 DEG C of constant temperature stirring 0.5h, filtration washing, by filter cake in 700 DEG C, 100% water vapour atmosphere Middle roasting 1h, obtains sieve sample C.The physico-chemical property of sieve sample C, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline group Table 2 is listed at result.

Embodiment 4

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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 simultaneously, 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 15 weight % molecular sieve pulp, additions concentration be 160g/L RECl₃Solution 100mL is warming up to 80 DEG C of constant temperature stirring 1h, filtration washing, by filter cake in 680 DEG C, 100% water vapour atmosphere Middle roasting 1h, obtains sieve sample D.The physico-chemical property of sieve sample D, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline group Table 2 is listed at result.

Embodiment 5

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.Gained molecular sieve is taken to roast 0.5h 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 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 citric acid 20g is added in stirring, 220g nitric 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 %, and 23gLiOH is added, and 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 be 20 weight % molecular sieve pulps, 5g oxalic acid is added in stirring, is then slowly added dropwise simultaneously 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 extremely It is neutral；By filter cake plus water be beaten solid content 15 weight % molecular sieve pulp, be added concentration be 160g/L RECl₃Solution 40mL, is warming up to 80 DEG C of constant temperature stirring 1h, and filter cake is roasted 2.5h in 650 DEG C, 100% water vapour atmosphere, obtained by filtration washing To sieve sample E.The physico-chemical property of sieve sample E, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline composition result are listed in table 2。

Embodiment 6

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.Gained molecular sieve is taken to roast 0.5h 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 600 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 45g 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 %, and 46gKOH is added, and 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 be 20 weight % molecular sieve pulps, 6g ethylenediamine tetra-acetic acid is added in stirring, then simultaneously 90g nitric acid (mass fraction 10%) and 90g fluosilicic acid (concentration 20%) is slowly added dropwise, is warming up to 85 DEG C of constant temperature stirring 4h, filtering It washs to neutrality；By filter cake plus water be beaten solid content 15 weight % molecular sieve pulp, be added concentration be 160g/L RECl₃It is molten Liquid 130mL is warming up to 80 DEG C of constant temperature stirring 1h, and filter cake is roasted 5h in 650 DEG C, 100% water vapour atmosphere by filtration washing, Obtain sieve sample F.The physico-chemical property of sieve sample F, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline composition result are listed in Table 2.

Comparative example 3

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %；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, filtration washing to neutrality；Filter cake plus water are beaten to obtain solid content 10 The RECl that concentration is 60g/L is added in the molecular sieve pulp of weight %₃Solution (mixed chlorinated rare earth solution, wherein in terms of oxide La₂O₃Account for 36 heavy %, CeO₂Account for 64 heavy %) 120mL, be warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake 550 DEG C, 6h is roasted in 100% water vapour atmosphere, obtains sieve sample DA1, physico-chemical property, the heavy oil of sieve sample DA1 is micro- counter to be commented Valence heavy oil conversion rate, gasoline, yield of liquefied gas are listed in table 3.

Comparative example 4

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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 to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, be added concentration be 60g/L RECl₃ Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide₂O₃Account for 36 heavy %, CeO₂Account for 64 heavy %) 120mL, it is warming up to 60 DEG C constant temperature stirs 1h, and filter cake is roasted 6h in 550 DEG C, 100% water vapour atmosphere, obtains sieve sample by filtration washing Physico-chemical property, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline, the yield of liquefied gas of DA2, sieve sample DA2 are listed in table 3.

Comparative example 5

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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, filtration washing to neutrality；Filter cake plus water are beaten to obtain the weight of solid content 10 % The RECl that concentration is 60g/L is added in molecular sieve pulp₃Solution (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 steams filter cake in 550 DEG C, 100% water 6h is roasted in vapour atmosphere, obtains sieve sample DA3, the physico-chemical property of sieve sample DA3, heavy oil micro anti-evaluation heavy oil conversion Rate, gasoline, yield of liquefied gas are listed in table 3.

Comparative example 6

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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 to neutrality；Filter cake plus water are beaten Starch solid content 10 weight % molecular sieve pulp, be added concentration be 60g/L RECl₃Solution (mixed chlorinated rare earth solution, wherein The La in terms of oxide₂O₃Account for 36 heavy %, CeO₂Account for 64 heavy %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing will be filtered Cake roasts 6h in 550 DEG C, 100% water vapour atmosphere, obtains sieve sample DA4, the physico-chemical property of sieve sample DA4, Heavy oil micro anti-evaluation heavy oil conversion rate, gasoline, yield of liquefied gas are listed in table 3.

Comparative example 7

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add Enter the RECl that concentration is 60g/L₃Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide₂O₃Account for 36 heavy %, CeO₂Account for 64 Weight %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing roasts filter cake in 550 DEG C, 100% water vapour atmosphere 6h obtains sieve sample DA5, the physico-chemical property of sieve sample DA5, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline, liquefaction Gas yield is listed in table 3.

Comparative example 8

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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, filtration washing to neutrality；By filter cake plus water be beaten solid content 10 weight % molecular sieve pulp, add Enter the RECl that concentration is 60g/L₃Solution (mixed chlorinated rare earth solution, wherein the La in terms of oxide₂O₃Account for 36 heavy %, CeO₂Account for 64 Weight %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing roasts filter cake in 550 DEG C, 100% water vapour atmosphere 6h obtains sieve sample DA6, the physico-chemical property of sieve sample DA6, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline, liquefaction Gas yield is listed in table 3.

Comparative example 9

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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, filtration washing to neutrality；Filter cake plus water are beaten to obtain solid content 10 The RECl that concentration is 60g/L is added in the molecular sieve pulp of weight %₃Solution (mixed chlorinated rare earth solution, wherein in terms of oxide La₂O₃Account for 36 heavy %, CeO₂Account for 64 heavy %) 120mL, be warming up to 60 DEG C of constant temperature stirring 1h, filtration washing, by filter cake 550 DEG C, 6h is roasted in 100% water vapour atmosphere, obtains sieve sample DA7, physico-chemical property, the heavy oil of sieve sample DA7 is micro- counter to be commented Valence heavy oil conversion rate, gasoline, yield of liquefied gas are listed in table 3.

Comparative example 10

By Y molecular sieve (production of catalyst asphalt in Shenli Refinery, 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 content for measuring molecular sieve is small In 5 heavy %.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 to neutrality；By filter cake plus water Be beaten solid content 10 weight % molecular sieve pulp, be added concentration be 60g/L RECl₃Solution (mixed chlorinated rare earth solution, In the La in terms of oxide₂O₃Account for 36 heavy %, CeO₂Account for 64 heavy %) 120mL, 60 DEG C of constant temperature stirring 1h are warming up to, filtration washing will Filter cake roasts 6h in 550 DEG C, 100% water vapour atmosphere, obtains sieve sample DA8, the materialization of sieve sample DA8 Matter, heavy oil micro anti-evaluation heavy oil conversion rate, gasoline, yield of liquefied gas are listed in table 3.

For the Y molecular sieve after alkali process desiliconization it can be seen from data in table 3, using single organic acid oxalic acid dealuminzation (DA5), 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) 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.When fluosilicic acid dealuminzation is used alone (DA3), the Y molecular sieve of available high silica alumina ratio, but strong acid institute's accounting in total acid Example is lower, and B acid/L acid ratio is lower.Fluosilicic acid composite organic acid oxalic acid dealuminzation (DA7) is equally unable to get preferable acid point Cloth.Fluosilicic acid composite inorganic acid HCl dealumination (DA8), strong acid proportion and B acid/L acid ratio in total acid are all not so good as this The open molecular sieve provided is high.The disclosure uses compound acid system, under three kinds of sour synergistic effects, can guarantee molecular sieve Aluminium distribution is effectively adjusted under the premise of crystal structure and mesopore orbit structural intergrity, improves acid distribution, and molecular sieve surface is rich Silicon can inhibit the generation of the non-selective side reaction in surface, mesoporous abundant, is conducive to the progress of residual oil cracking reaction, can be improved weight Oily conversion ratio reduces coke yield, reduces content of olefin in gasoline.

Table 1

Title	Numerical value
		Density (20 DEG C), g/cm³	0.9154
Refractive power (70 DEG C)	0.4926
		Viscosity (50 DEG C), mm²/s	34.14
Viscosity (70 DEG C), mm²/s	6.962
		Acid value, mgKOH/g	0.27
Freezing point, DEG C	35
		Aniline point, DEG C	82
Carbon residue, m%	0.18
		Four components
Saturated hydrocarbons, m%	64.0
		Aromatic hydrocarbons	32.0
Colloid	4.0
		Asphalitine	0.0
Tenor, ppm
		Ni	<0.1
V	<0.1
		Cu	0.1
Fe	0.5
		Na	0.8
H, %	12.03
		C, %	85.38
S, %	2.0
		N, %	0.16
IBP, DEG C/5%	329/363
		10%/30%	378/410
50%/70%	436/462
		90%/95%	501/518

Table 2

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 3

Claims

1. a kind of Y molecular sieve containing rare earth, the cell parameter of the molecular sieve is 24.35-24.55 angstroms；With RE₂O₃It counts and with molecule On the basis of the dry weight of sieve, the content of rare earth of the molecular sieve is 0.5-19 weight %；The Al distribution parameter D of the molecular sieve is full Foot: 0.4≤D≤0.9, wherein D=Al (S)/Al (C), Al (S) indicate the zeolite crystal measured using TEM-EDS method The inside H in crystal face edge indicates to survey using TEM-EDS method apart from interior any aluminium content for being greater 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 greater than 100 square nanometers regions, Described in H be the crystal face edge point to the crystal face geometric center distance 10%；The mesopore volume Zhan of the molecular sieve is total The ratio of pore volume be 25-65%, it is described it is mesoporous for aperture be greater than 2 nanometers of molecular sieve pore passages less than 100 nanometers；The molecule The ratio that the strong acid acid amount of sieve accounts for total acid content is 60-90%, and the ratio between B acid acid amount and L acid acid amount are 20-100；The molecular sieve 's²⁷In Al MAS H NMR spectroscopy, chemical shift be the peak area of 60ppm ± 2ppm resonance signal and chemical shift be 55ppm ± The ratio between peak area of 2ppm resonance signal is (1.5-5): 1, chemical shift is the face peak area Zhan Zong Feng of 0 ± 2ppm resonance signal Long-pending ratio is not more than 5%.

2. the Y molecular sieve according to claim 1 containing rare earth, wherein the cell parameter of the molecular sieve is 24.40- 24.52 angstroms；With RE₂O₃It counts and on the basis of the dry weight of molecular sieve, the content of rare earth of the molecular sieve is 3-16 weight %；Institute The Al distribution parameter D for stating molecular sieve 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 ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 65-85%, and the ratio between B acid acid amount and L acid acid amount are 35- 75；The molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift is the peak area and chemical potential of 60ppm ± 2ppm resonance signal Shifting is that the ratio between peak area of 55ppm ± 2ppm resonance signal is (2-4): 1, chemical shift is the peak face of 0 ± 2ppm resonance signal Product accounts for the ratio of total peak area no more than 3%.

3. the Y molecular sieve according to claim 1 containing rare earth, wherein the rare earth is in lanthanum, cerium, praseodymium and neodymium It is at least one.

4. the Y molecular sieve according to claim 1 containing rare earth, wherein the strong acid acid amount of the molecular sieve accounts for total acid content Ratio uses NH₃- TPD method measures, and the acid site of the strong acid is NH₃Desorption temperature be greater than 300 DEG C corresponding in acid The heart；The ratio between the B acid acid amount and L acid acid amount are measured using the infrared acid process of pyridine adsorption；The molecular sieve²⁷Al The peak area of resonance signal is calculated using integration method in MAS H NMR spectroscopy.

5. the preparation method of the Y molecular sieve containing rare earth described in a kind of any one of claim 1-4, the preparation method packet It 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 Carry out the second dealumination treatment in liquid, and after being filtered and washed, obtain the second dealuminzation molecular sieve, inorganic acid be selected from hydrochloric acid, At least one of sulfuric acid and nitric acid；

G, the second dealuminzation molecular sieve of gained in step f is subjected to impregnation in the dipping solution containing compounds containing rare earth, And after being filtered, washed and carrying out hydrothermal calcine processing in steam atmosphere, the Y molecular sieve containing rare earth is obtained.

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, inorganic acid are in hydrochloric acid, sulfuric acid and nitric acid At least one.

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.

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 compounds containing rare earth described in step g be selected from containing lanthanum, The chlorate and/or nitrate of at least one of cerium, praseodymium and neodymium.

15. preparation method according to claim 5, wherein the condition of impregnation described in step g includes: with RE₂O₃ The rare earth of meter and with the weight ratio of the molecular sieve of dry basis be (0.11-0.32): 1, the dipping solution with dry basis The weight ratio of the molecular sieve of meter is (6-25): 1；The temperature of the impregnation is 30-90 DEG C, and the time of impregnation is 0.5-3 hours.

16. preparation method according to claim 5, wherein the condition of the processing of hydrothermal calcine described in step g includes: temperature Degree is 450-750 DEG C, and the time is 0.5-6 hours, and steam atmosphere is the vapor of 100 volume %.