CN107971008A

CN107971008A - A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method

Info

Publication number: CN107971008A
Application number: CN201610921278.1A
Authority: CN
Inventors: 王丽霞; 田辉平; 刘宇键; 周治; 袁帅; 孙敏; 欧阳颖; 庄立
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-21
Filing date: 2016-10-21
Publication date: 2018-05-01
Anticipated expiration: 2036-10-21
Also published as: CN107971008B

Abstract

This disclosure relates to a kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method, on the basis of the butt weight of the catalyst, the catalyst is included with the BEA structure molecular screens of 24 75 weight % of dry basis, with the natural clay of 5 65 weight % of dry basis, the inorganic oxide binder of in terms of oxide 10 60 weight %, with P₂O₅Count the phosphorus additive of 0.1 15 weight %, and the metallic addition of in terms of the oxide of metal 0.1 15 weight %, the ratio that the mesoporous Bronsted acid amount of the catalyst accounts for total acid content is 20 70%.The catalytic cracking catalyst is used for having higher low-carbon alkene and BTX yields in petroleum hydrocarbon catalytic pyrolysis.

Description

A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method

Technical field

This disclosure relates to a kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method.

Background technology

The low-carbon alkenes such as ethene, propylene, butylene are essential industrial chemicals, can be used to synthetic resin, fiber and rubber Glue etc..Wherein, propylene is a kind of important source material for being used to manufacture petroleum chemicals for being only second to ethene, mainly for the production of poly- third The chemical products such as alkene, acrylonitrile, propylene oxide.Production of propylene is mainly derived from pair when thermal cracking produces ethene both at home and abroad at present Product, second largest source are FCC apparatus.FCC apparatus provides 30% or so of propylene demand, in the U.S., FCC apparatus production Propylene then provide half of the petroleum chemicals to propylene demand.

In recent years, the demand rapid development of propylene, it was predicted that by 2016, the growth rate of global propylene consumption will More than ethene, reach 5% or so.But the propylene/ethylene of steam cracking ratio cannot be adjusted flexibly, and its reaction temperature is up to 840-860 DEG C, energy expenditure accounts for the 40% of petrochemical industry energy consumption.Therefore, it is for meeting come a large amount of propylene enhancings by FCC The effective and efficient approach that propylene demand increases.

Beta molecular sieves are a kind of high silicon large pore molecular sieves, are synthesized first in 1967 by Mobil companies.1988 Year, Newsman and Kiggins determine beta by modern technologies such as electronic diffraction, high resolution electron microscope and computers The crystal structure of molecular sieve.Structural research shows that Beta molecular sieves have three cross one another 12 membered ring channels, parallel to (001) the twelve-ring aperture of the one-dimensional channels of crystal face is 0.57~0.75nm, another the two-dimentional holes parallel with (100) crystal face The twelve-ring aperture in road is 0.56~0.65nm.Due to the pore passage structure of Beta molecular sieves uniqueness, peracidity and good water Heat endurance, the prospect of its commercial Application is extensive, has been applied successfully to the stones such as the alkylation of isomerization, catalytic cracking and aromatic hydrocarbons Oily chemical field.

Chinese patent CN103785460A discloses a kind of catalyst for producing low-carbon alkene and preparation method thereof, uses The catalyst system of the Beta molecular sieves of MFI structure molecular sieve and P Modification compounding, has for naphtha catalytic cracking propylene There is the productivity of low carbon olefin hydrocarbon of higher.

Chinese patent CN103509588A disclose it is a kind of be directed to containing the more feedstock oil low-carbon olefines high-output of naphthenic ring and The cracking method of light aromatic hydrocarbons, is compounded using Beta molecular sieves and MFI structure molecular sieve, and Beta molecular sieves and MFI molecular sieves Weight ratio is not less than 1/3.This method has higher propylene and an isobutene yield, and BTX ratios are higher in gasoline fraction aromatic hydrocarbons.

Chinese patent CN102533315A uses modified Y molecular sieve, modified Beta system with molecular sieve for preparing into catalyst, for being catalyzed Cracked diesel oil hydrogenation aromatics-removing, desulfurization degree and denitrification percent take off virtue rate up to more than 55%, diesel oil distillate yield up to more than 97.5% Up to more than 98wt%.

Chinese patent CN102451753A improves octane number using Beta molecular sieves.

But since the molecular sieve in catalyst has shape-selective effect, when the aerodynamic size of reactant molecule is more than micropore point During the aperture of son sieve, reactant molecule can not be diffused into inside molecular sieve, influence reactivity.Therefore researcher directly closes Into the Beta molecular screen materials containing multi-stage porous or first catalyst will be made again after molecular sieve reaming, to improve its duct knot Structure.But during catalyst is prepared, the mesoporous of molecular sieve can be blocked by matrix, greatly reduce the mesoporous effect of molecular sieve Rate, or even the mesoporous performance of molecular sieve is not gone out effect.

The content of the invention

The purpose of the disclosure is to provide a kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method, The catalytic cracking catalyst is used for having higher low-carbon alkene and BTX yields in petroleum hydrocarbon catalytic pyrolysis.

To achieve these goals, disclosure first aspect：A kind of catalytic cracking catalyst is provided, with the catalyst On the basis of butt weight, which is included with the BEA structure molecular screens of dry basis 24-75 weight %, with butt weight Count the natural clay of 5-65 weight %, the inorganic oxide binder of the weight of the 10-60 in terms of oxide %, with P₂O₅Count 0.1-15 The phosphorus additive of weight %, and the metallic addition of the weight of the 0.1-15 in terms of the oxide of metal %, the catalyst it is mesoporous The ratio that Bronsted acid amount accounts for total acid content is 20-70%.

Preferably, with P₂O₅Count and on the basis of the butt weight of the catalyst, the content of the phosphorus additive is 0.5- 6.5 weight %, are counted and on the basis of the butt weight of the catalyst, the content of the metallic addition by the oxide of metal For 0.5-10 weight %.

Preferably, total specific surface area of the catalyst is 240-350m²/ g, mesoporous Bronsted acid amount account for the ratio of total acid content For 25-50%.

Preferably, the mesopore volume of the catalyst is 0.14-0.35ml/g, and the ratio that mesopore volume accounts for total pore volume is 35-60%.

Preferably, the natural clay is selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave rod stone, sea At least one of afrodite, galapectite, hydrotalcite, bentonite and rectorite；The inorganic oxide binder is selected from oxidation At least one of silicon, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.

Preferably, the metal is selected from least one of iron, cobalt, nickel, copper, manganese, zinc, tin and titanium.

Preferably, total specific surface area, mesopore volume and the total pore volume of the catalyst use N2 adsorption BET specific surface area Method measures；The mesoporous Bronsted acid amount is adsorbed infrared acid process using 2,6- di-tert-butyl pyridines and is measured, institute Give an account of hole Bronsted acid and refer to that kinetic diameter isThe Bronsted acid that can touch of 2,6 di tert butyl pyridine molecule；Institute State total acid content and use NH₃- TPD methods measure.

Disclosure second aspect：A kind of method for preparing catalytic cracking catalyst is provided, this method comprises the following steps：a、 BEA structure molecular screens, natural clay, inorganic oxide binder presoma and water are mixed and are beaten uniformly, then by gained Slurries are spray-dried, and obtain spray dried microspheres, wherein, on the basis of total butt weight of spray dried microspheres, the spraying Dry microspheres are included with the BEA structure molecular screens of dry basis 25-75 weight %, with the day of dry basis 5-65 weight % Right clay, and the inorganic oxide binder presoma of the weight of the 10-60 in terms of oxide %；B, described in being obtained in step a Spray dried microspheres carry out alkali process, and after being filtered and being washed, obtain the material after alkali process；C, will be obtained in step b The alkali process after material in the Compound-acid solution being made of fluosilicic acid, organic acid and inorganic acid at acid for composite Reason, and after being filtered and being washed, obtain the material after compound acid treatment；D, the compound acid treatment that will be obtained in step c After material afterwards carries out P Modification processing, carried metal processing and the first calcination process, catalytic cracking catalyst is obtained, wherein, With P₂O₅Count and on the basis of the butt weight of the catalyst, the content of phosphorus additive is 0.1-15 weight %, with the oxygen of metal Compound meter and on the basis of the butt weight of the catalyst, the content of metallic addition is 0.1-15 weight %；Wherein, it is described The ratio that the mesoporous Bronsted acid amount of catalyst accounts for total acid content is 20-70%.

Preferably, the natural clay in step a is selected from kaolin, halloysite, montmorillonite, diatomite, convex At least one of recessed rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite；Before the inorganic oxide binder It is selected from least one of Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol to drive body.

Preferably, the alkali process in step b includes：The spray dried microspheres are mixed with alkaline solution, it is described Alkaline solution is in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonium hydroxide and high alkali deflection aluminium acid sodium solution At least one.

Preferably, the condition of the mixing includes：With in the spray dried microspheres and alkaline solution of dry basis Alkali weight ratio be 1：(0.01-0.35)；Wherein, the weight of the alkali in the sodium hydroxide solution is with the weight of sodium hydroxide Count, the weight of the alkali in the potassium hydroxide solution is in terms of the weight of potassium hydroxide, the weight of the alkali in the lithium hydroxide solution Amount is in terms of the weight of lithium hydroxide, and the weight of the alkali in the ammonium hydroxide is in terms of the weight of a hydration ammonia, the high alkali deflection aluminium acid sodium The weight of alkali in solution is in terms of the weight of sodium oxide molybdena.

Preferably, using the weight ratio of the alkali in the spray dried microspheres and alkaline solution of dry basis as 1： (0.05-0.25)。

Preferably, the organic acid in step c is selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid At least one of, the inorganic acid is selected from least one of hydrochloric acid, sulfuric acid and nitric acid.

Preferably, the condition of the compound acid treatment in step c is：With the thing after the alkali process of dry basis Material, fluosilicic acid, the weight ratio of inorganic acid and organic acid are 1：(0.01-0.45)：(0.01-0.45)：(0.01-0.55).

Preferably, the condition of the compound acid treatment in step c is：With the thing after the alkali process of dry basis Material, fluosilicic acid, the weight ratio of inorganic acid and organic acid are 1：(0.05-0.3)：(0.1-0.3)：(0.1-0.3).

Preferably, this method further includes：Material after the compound acid treatment obtained in step c is subjected to the second roasting Processing, obtains the material after the second calcination process, then carries out ammonium exchange processing to the material after second calcination process, obtains Material after being handled to ammonium exchange, then carries out the P Modification processing, carried metal processing and the first calcination process again.

Preferably, the condition of second calcination process includes：The atmosphere of second calcination process is air atmosphere or nitrogen Atmosphere or steam atmosphere；The temperature of roasting is 400-800 DEG C, when the time of roasting is 0.5-8 small.

Preferably, the ammonium exchanges processing and causes, in terms of sodium oxide molybdena and with total dry basis of the catalytic cracking catalyst On the basis of amount, the sodium content of the catalytic cracking catalyst is less than 0.15 weight %；The ammonium exchange processing includes：By described Material after two calcination process is mixed with ammonium salt, and the ammonium salt is selected from ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, acetic acid At least one of ammonium and ammonium nitrate.

Preferably, the P Modification processing in step d includes：Phosphorus-containing compound impregnates molecular sieve and/or Ion exchange, the phosphorus-containing compound are selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

Preferably, the carried metal processing in step d includes：By dipping method by the chemical combination containing carried metal The carried metal of thing is loaded on catalyst, and the carried metal is in iron, cobalt, nickel, copper, manganese, zinc, tin and titanium At least one, the compound containing carried metal are the water soluble salt containing the carried metal.

Preferably, the compound containing carried metal is selected from the sulfate containing the carried metal, nitrate At least one of with chlorate.

Preferably, the condition of first calcination process in step d includes：The atmosphere of first calcination process is air gas Atmosphere or nitrogen atmosphere or steam atmosphere；The temperature of roasting is 400-800 DEG C, when the time of roasting is 0.5-8 small.

The disclosure third aspect：A kind of catalytic cracking catalyst is provided, which is by the disclosure second What the method that aspect provides was prepared.

Disclosure fourth aspect：A kind of method of petroleum hydrocarbon catalytic pyrolysis is provided, this method includes：In the bar of catalytic pyrolysis Under part, the catalytic cracking catalyst that petroleum hydrocarbon is provided with the disclosure first or the third aspect is set to carry out haptoreaction.

Through the above technical solutions, the catalytic cracking catalyst that the disclosure provides is used in petroleum hydrocarbon catalytic pyrolysis be conducive to Improve the yield of low-carbon alkene especially propylene and BTX.

Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.

Embodiment

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

Disclosure first aspect：A kind of catalytic cracking catalyst is provided, should on the basis of the butt weight of the catalyst Catalyst is included with the BEA structure molecular screens of dry basis 24-75 weight %, with the natural of dry basis 5-65 weight % Clay, the inorganic oxide binder of the weight of the 10-60 in terms of oxide %, with P₂O₅The phosphorus additive of 0.1-15 weight % is counted, and The metallic addition of the weight of the 0.1-15 in terms of the oxide of metal %, the mesoporous Bronsted acid amount of the catalyst account for the ratio of total acid content Example is 20-70%.Further, on the basis of the butt weight of the catalyst, which is included with dry basis 29- The BEA structure molecular screens of 55 weight %, with the natural clay of dry basis 8-50 weight %, the weights of the 20-50 in terms of oxide The inorganic oxide binder of % is measured, with P₂O₅Count the phosphorus additive of 0.5-6.5 weight %, and the 0.5- in terms of the oxide of metal The metallic addition of 10 weight %.Yet further, total specific surface area of the catalyst is 240-350m²/ g, mesoporous proton The ratio that acid amount accounts for total acid content is 25-50%.Further, the mesopore volume of the catalyst is 0.14-0.35ml/g, is situated between The ratio that pore volume accounts for total pore volume is 35-60%.The catalytic cracking catalyst that disclosure first aspect is provided has abundant Meso-hole structure and excellent hydrothermal stability, suitable for the catalytic cracking reaction of petroleum hydrocarbon, low-carbon alkene can be improved especially It is propylene and the yield of BTX.Catalysis of the catalytic cracking catalyst that disclosure first aspect provides especially suitable for naphtha Cracking reaction, can significantly improve the yield of BTX and propylene.

According to the disclosure in a first aspect, the BEA structure molecular screens are well-known to those skilled in the art, Ke Yiwu , can also be by gained after the molecular sieve roasting of template agent method preparation, for example, Beta molecular sieves obtained by amine crystallization.

According to the disclosure in a first aspect, the natural clay can be it is commonly used in the art, be preferably selected from height In ridge soil, halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite At least one.The inorganic oxide binder can be commonly used in the art, be preferably selected from silica, oxidation At least one of aluminium, zirconium oxide, titanium oxide and amorphous silica-alumina.

According to the disclosure, the metal of the metallic addition refers to load to the metal on molecular sieve by mode of loading, Do not include the alkali metal such as aluminium and sodium, potassium, can include selected from least one of iron, cobalt, nickel, copper, manganese, zinc, tin and titanium, It can include other metals, the present invention is simultaneously not limited.

According to the disclosure, total specific surface area, mesopore volume and the total pore volume of the catalyst compare table using N2 adsorption BET Area method measures, and the AS-3 produced using Quantachrome instrument companies, AS-6 static state n2 absorption apparatus is measured, Specific method is：Sample is placed in sample processing system, 1.33 × 10 are evacuated at 300 DEG C^-2Pa, heat-insulation pressure keeping 4h, only Change 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 de- Attached amount, obtains N₂Adsorption-desorption isothermal curve, then calculates total specific surface area using two parameter BET formula, takes than pressing P/P₀= Less than 0.98 adsorbance is the total pore volume of sample, and the pore-size distribution of mesoporous part is calculated using BJH formula, and using integration Method calculates mesopore volume.The mesoporous Bronsted acid amount is adsorbed infrared acid process using 2,6- di-tert-butyl pyridines and is measured, Such as the Vertex70 model instruments of Bruker instrument companies production can be used to be measured, specific method is：By catalyst It is pressed into 10mg/cm²Thin slice, be put into band CaF₂In the infrared pond of window, first vacuumized at 400 DEG C, then drop to 150 DEG C of absorption 2, 6- di-tert-butyl pyridines 15 minutes, then vacuumize 1 it is small when, drop to room temperature collection spectrogram, and calculate Bronsted acid amount.Referring to Applied Catalysis A:General, 294,2005：92.The implication of the mesoporous Bronsted acid is those skilled in the art It is known, refer to that kinetic diameter isThe Bronsted acid that can touch of 2,6 di tert butyl pyridine molecule.It is described total Acid amount uses NH₃- TPD methods measure, such as can be taken off using II 2920 temperature programmings of Merck ＆ Co., Inc of U.S. Autochem Attached instrument is measured, and specific method is：Weigh 0.2g samples to be tested and load sample cell, be placed in conductance cell heating furnace, He gas is load Gas (50mL/min), is warming up to 600 DEG C, purging 60min drives away the impurity of catalyst surface absorption, so with the speed of 20 DEG C/min After be cooled to 100 DEG C, constant temperature 30min, switches to NH₃- He gaseous mixtures (10.02%NH₃+ 89.98%He) absorption 30min, followed by Continuous with He air-blowings to sweep 90min steady to baseline, to be desorbed the ammonia of physical absorption；600 are warming up to 10 DEG C/min heating rates DEG C it is desorbed, keeps 30min, desorption terminates；Using TCD detector detection gas change of component, instrument automatic integration obtains Total acid content.

Disclosure second aspect：A kind of method for preparing catalytic cracking catalyst is provided, this method comprises the following steps：a、 BEA structure molecular screens, natural clay, inorganic oxide binder presoma and water are mixed and are beaten uniformly, then by gained Slurries are spray-dried, and obtain spray dried microspheres, such as according to BEA structure molecular screens in terms of butt, natural in terms of butt Clay, the inorganic oxide binder presoma in terms of oxide=(25-75)：(5-65)：(10-60) is preferred (30-55)： (8-50)：The weight ratio of (20-50) mixes BEA structure molecular screens, natural clay, inorganic oxide binder presoma and water Close, mashing, spray drying, obtain spray dried microspheres；Wherein, it is described on the basis of total butt weight of spray dried microspheres Spray dried microspheres are included with the BEA structure molecular screens of dry basis 25-75 weight %, with dry basis 5-65 weight % Natural clay, and the inorganic oxide binder presoma of the weight of the 10-60 in terms of oxide %；Preferably, with spray drying On the basis of total butt weight of microballoon, the spray dried microspheres include the BEA structures point with dry basis 30-55 weight % Son sieve, is bonded with the inorganic oxide of the natural clay of dry basis 8-50 weight %, and the weight of the 20-50 in terms of oxide % Agent presoma；B, the spray dried microspheres obtained in step a are subjected to alkali process, and after being filtered and being washed, obtained Material after alkali process；Material after the alkali process that will be obtained in step b is formed by fluosilicic acid, organic acid and inorganic acid Compound-acid solution in acid treatment for composite, and after being filtered and being washed, obtain the material after compound acid treatment；D, will step After material after the compound acid treatment obtained in rapid c carries out P Modification processing, carried metal processing and the first calcination process, Catalytic cracking catalyst is obtained, wherein, with P₂O₅Count and on the basis of the butt weight of the catalyst, the content of phosphorus additive For 0.1-15 weight %, counted by the oxide of metal and on the basis of the butt weight of the catalyst, metallic addition contains Measure as 0.1-15 weight %；Wherein, the ratio that the mesoporous Bronsted acid amount of the catalyst accounts for total acid content is 20-70%.Further Ground, with P₂O₅To count and on the basis of the butt weight of the catalyst, the content of the phosphorus additive is 0.5-6.5 weight %, with The oxide meter of metal and on the basis of the butt weight of the catalyst, the content of the metallic addition is 0.5-10 weights Measure %.Total specific surface area of the catalyst is 240-350m²/ g, the ratio that mesoporous Bronsted acid amount accounts for total acid content are 25-50%. Further, the mesopore volume of the catalyst is 0.14-0.35ml/g, and the ratio that mesopore volume accounts for total pore volume is 35- 60%.

The inventor of the disclosure is it was unexpectedly observed that first by conventional Beta system with molecular sieve for preparing into passing through soda acid again after catalyst microspheres The method of coupling processing carries out modulation to the pore passage structure of molecular sieve, it is ensured that it is newly-generated it is mesoporous be not plugged so that Catalyst has larger specific surface area and mesopore volume, improves the stability of catalyst, which is used for petroleum hydrocarbon Be conducive to improve the yield of low-carbon alkene especially propylene and BTX in catalytic pyrolysis.

According to the second aspect of the disclosure, the natural clay in step a can be it is commonly used in the art, preferably For selected from kaolin, halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and At least one of rectorite；The inorganic oxide binder presoma can be commonly used in the art, preferably select From at least one of Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.

According to the second aspect of the disclosure, in step a, after obtaining spray dried microspheres, can also include doing the spraying Dry microballoon carries out the step of three calcination process, and the condition of the 3rd calcination process can include：The atmosphere of roasting is air Atmosphere or nitrogen atmosphere or steam atmosphere, steam atmosphere are 1-100% vapor, preferably 100% vapor；The temperature of roasting Spend for 400-800 DEG C, be preferably 500-600 DEG C, time of roasting be at least 0.5 it is small when, when being preferably 0.5-8 small.

According to the second aspect of the disclosure, the alkali process in step b can include：By the spray dried microspheres with Alkaline solution mixes.The alkaline solution can be selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, hydrogen At least one of ammonium hydroxide solution and high alkali deflection aluminium acid sodium solution, are preferably high alkali deflection aluminium acid sodium solution.When the alkalescence is molten When liquid is high alkali deflection aluminium acid sodium solution, in terms of oxide, the sodium content of the high alkali deflection aluminium acid sodium solution can be 270-310 G/l, aluminium content can be 30-50 g/l, and the density of high alkali deflection aluminium acid sodium solution can be 1.25-1.45 grams per milliliters.Institute Stating the condition of mixing can include：Using the weight ratio of the alkali in the spray dried microspheres and alkaline solution of dry basis as 1:(0.01-0.35), further, with the weight ratio of the alkali in the spray dried microspheres and alkaline solution of dry basis For 1:(0.05-0.25)；Wherein, the weight of the alkali in the sodium hydroxide solution is in terms of the weight of sodium hydroxide, the hydrogen-oxygen Change the weight of the alkali in potassium solution in terms of the weight of potassium hydroxide, the weight of the alkali in the lithium hydroxide solution is with lithium hydroxide Weight meter, the weight of the alkali in the ammonium hydroxide in terms of the weight of a hydration ammonia, alkali in the high alkali deflection aluminium acid sodium solution Weight is in terms of the weight of sodium oxide molybdena.The content of water in the alkaline solution does not have special limitation, for example, with dry basis Spray dried microspheres and alkaline solution in water weight ratio can be 1：(5-15).

According to the second aspect of the disclosure, the temperature of alkali process can be 25-100 DEG C, and the time of alkali process can be When 0.5-6 is small.

According to the second aspect of the disclosure, the compound acid treatment in step c can carry out once or several times, can be with First organic acid is mixed with the material after the alkali process, then mixes fluosilicic acid and inorganic acid with the material after the alkali process Close, you can with first to add organic acid in the material after alkali process, then by fluosilicic acid and inorganic acid, cocurrent adds at a slow speed, or First add fluosilicic acid and add inorganic acid, be preferably that cocurrent adds at a slow speed for fluosilicic acid and inorganic acid.The organic acid in step c It can be selected from least one of ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfosalicylic acid, be preferably oxalic acid or lemon Acid, more preferably oxalic acid.The inorganic acid can be selected from least one of hydrochloric acid, sulfuric acid and nitric acid, be preferably salt Acid or sulfuric acid, more preferably hydrochloric acid.

According to the second aspect of the disclosure, the condition of the compound acid treatment in step c can be：With dry basis The alkali process after material, fluosilicic acid, the weight ratio of inorganic acid and organic acid be 1:(0.01-0.45):(0.01- 0.45):(0.01-0.55), further, with the material after the alkali process of dry basis, fluosilicic acid, inorganic acid and has The weight ratio of machine acid is 1:(0.05-0.3):(0.1-0.3):(0.1-0.3).The Compound-acid treatment temperature can be 25- 100 DEG C, when processing time can be 0.5-6 small.

According to the second aspect of the disclosure, in order to reduce the sodium content of catalyst, this method can also include：By step c In material after the obtained compound acid treatment carry out the second calcination process, obtain the material after the second calcination process, then Ammonium exchange processing is carried out to the material after second calcination process, the material after ammonium exchange processing is obtained, then carries out institute again State P Modification processing, carried metal processing and the first calcination process.Second calcination process is that those skilled in the art institute is ripe Know, for example, the condition of second calcination process can include：The atmosphere of second calcination process is air atmosphere or nitrogen gas Atmosphere or steam atmosphere, steam atmosphere are 1-100% vapor, preferably 100% vapor；The temperature of calcination process is 400- 800 DEG C, be preferably 500-600 DEG C, time of calcination process be at least 0.5 it is small when, when being preferably 0.5-8 small.

According to the second aspect of the disclosure, the ammonium exchange processing is well-known to those skilled in the art, for example, described Ammonium exchange processing can include：Material after the calcination process is mixed with ammonium salt, can be according to the institute of dry basis State the material after calcination process：Ammonium salt：H₂O=1：(0.1-1)：The weight ratio of (5-10) is in room temperature to exchanging 0.5-2 at 100 DEG C Filtered after hour, this exchange process repeats 1-4 times so that in terms of sodium oxide molybdena and with total dry basis of the catalytic cracking catalyst On the basis of amount, the sodium content of the catalytic cracking catalyst is less than 0.15 weight %.The ammonium salt can be common Inorganic Ammonium Salt, for example, the ammonium salt can be in ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate and ammonium nitrate extremely Few one kind.

According to the second aspect of the disclosure, the processing of the P Modification in step d be it is well-known to those skilled in the art, For example, the P Modification processing can include：Phosphorus-containing compound impregnates molecular sieve and/or ion exchange, it is described to contain Phosphorus compound can be selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

According to the second aspect of the disclosure, the carried metal processing in step d is well known to those skilled in the art , refer to that carried metal is loaded on catalyst by mode of loading, for example, can will contain selected from iron, cobalt, nickel, copper, manganese, The compound of at least one of zinc, tin and titanium carried metal is loaded to the carried metal on catalyst by dipping method, Compound containing carried metal can be the water soluble salt of carried metal, be, for example, in sulfate, nitrate and chlorate At least one, the compound containing carried metal are preferably ferric sulfate, cobaltous sulfate, nickel sulfate, copper sulphate, manganese sulfate, sulphur Sour zinc, STANNOUS SULPHATE CRYSTALLINE, titanium sulfate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, manganese nitrate, zinc nitrate, nitric acid tin, Titanium Nitrate, chlorine Change at least one of iron, cobalt chloride, nickel chloride, copper chloride, manganese chloride, zinc chloride, stannic chloride and titanium chloride；The load side Formula can also include other common metal carrying methods, and the present invention is not restricted.

According to a kind of embodiment of disclosure second aspect, P Modification processing and carried metal processing can be with Using following three kinds of modes：

1st, by the material after the compound acid treatment obtained in step c and the phosphorus-containing compound aqueous solution of calculation amount in room Temperature is to 95 DEG C of mashing uniformly drying, after roasting under the conditions of 400-800 DEG C, then with the iron content of calculation amount, cobalt, nickel, copper, manganese, zinc, The compound water solution of at least one of tin and titanium carried metal is in room temperature to 95 DEG C of uniformly mixed, drying.

2nd, by the material after the compound acid treatment obtained in step c and the phosphorus-containing compound aqueous solution of calculation amount in room Temperature to 95 DEG C of mashing uniformly drying, then with least one of the iron content of calculation amount, cobalt, nickel, copper, manganese, zinc, tin and titanium carried metal Compound water solution room temperature to 95 DEG C be uniformly mixed drying, wherein can also will impregnate above two solution order top .

3rd, by the material after the compound acid treatment obtained in step c and the phosphorus-containing compound and iron content of calculation amount, cobalt, The mixed aqueous solution of the compound of at least one of nickel, copper, manganese, zinc, tin and titanium carried metal room temperature to 95 DEG C be uniformly mixed After dry；

When P Modification processing and carried metal processing are carried out in a manner of ion exchange, will typically be obtained in step c The compound acid treatment after material and calculation amount phosphorus-containing compound aqueous solution room temperature to 95 DEG C mashing uniformly drying, After being roasted under the conditions of 400-800 DEG C, then with least one of the iron content of calculation amount, cobalt, nickel, copper, manganese, zinc, tin and titanium gold-supported The compound water solution of category presses 1：The solid-to-liquid ratio of (5-20) after mixing, 80-95 DEG C stir 2-3 it is small when after filter, can weigh Reestablish diplomatic relations and change repeatedly, the washing of gained samples with water is multiple after exchange, drying.

According to the second aspect of the disclosure, first calcination process in step d is well known to those skilled in the art , for example, the condition of first calcination process can include：The atmosphere of first calcination process is air atmosphere or nitrogen atmosphere Or steam atmosphere, steam atmosphere are 1-100% vapor, preferably 100% vapor；The temperature of roasting is 400-800 DEG C, Preferably 500-600 DEG C, time of roasting be at least 0.5 it is small when, when being preferably 0.5-8 small.

Washing of the present invention is well-known to those skilled in the art, refers generally to wash, it is for instance possible to use 5-10 times The water of weight of material elutes material.

Disclosure fourth aspect：A kind of method of petroleum hydrocarbon catalytic pyrolysis is provided, this method includes：In the bar of catalytic pyrolysis Under part, the catalytic cracking catalyst that petroleum hydrocarbon is provided with the disclosure first or the third aspect is set to carry out haptoreaction.Preferably, institute Stating petroleum hydrocarbon includes naphtha.

Catalytic pyrolysis described in the disclosure is that the traditional handicraft in PETROLEUM PROCESSING field, its operating condition, raw material etc. is this Known to field technology personnel, unless otherwise instructed, its implication includes all petroleum hydrocarbon processing based on cracking reaction Technique, including the Deep Catalytic Cracking process for the purpose of producing in high-yield olefin.For example, the reaction condition of the catalytic pyrolysis can include： Reaction temperature can be 400-700 DEG C, and pressure can be 0-0.2 megapascal, and water-oil factor can be 0.2-1, the catalyst and stone The mass ratio of petroleum hydrocarbon can be (4-15)：1.

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

Influence of the catalytic cracking catalyst in petroleum hydrocarbon catalytic pyrolysis to productivity of propylene and BTX yields uses feedstock oil ACE is evaluated.By catalyst carry out 800 DEG C, 100% steam aging 14 it is small when handle, on fixed fluidized bed micro- anti-ACE devices Evaluated, feedstock oil is naphtha (composition and physical property be shown in Table 3), and appreciation condition is 630 DEG C of reaction temperature, regeneration temperature 670 DEG C, oil ratio is 10 (weight ratios).

Total specific surface area, mesopore volume and the total pore volume of catalyst are surveyed using N2 adsorption BET specific surface area method Amount, the AS-3 produced using Quantachrome instrument companies, AS-6 static state n2 absorption apparatus are measured, and specific method is：Will Sample is placed in sample processing system, and 1.33 × 10 are evacuated at 300 DEG C^-2Pa, heat-insulation pressure keeping 4h, purify sample；In liquid nitrogen At -196 DEG C of temperature, test purification sample is not pressing P/P on year-on-year basis₀Under the conditions of to the adsorbance and desorption rate of nitrogen, obtain N₂Inhale Attached-desorption isothermal curve, then calculates total specific surface area using two parameter BET formula, takes than pressing P/P₀Less than=0.98 suction Attached amount is the total pore volume of sample, the pore-size distribution of mesoporous part is calculated using BJH formula, and calculate mesoporous body using integration method Product.

Mesoporous Bronsted acid amount is adsorbed infrared acid process using 2,6- di-tert-butyl pyridines and is measured, using Bruker instrument The 70 model instruments of Vertex of device company production are measured, and specific method is：Catalyst is pressed into 10mg/cm²Thin slice, It is put into band CaF₂In the infrared pond of window, first vacuumized at 400 DEG C, then drop to 150 DEG C of 2,6- of absorption di-tert-butyl pyridines 15 and divide Clock, then vacuumize 1 it is small when, drop to room temperature collection spectrogram, and calculate Bronsted acid amount.Referring to Applied Catalysis A: General, 294,2005：92.

Total acid content uses NH₃- TPD methods measure, using II 2920 program liters of Merck ＆ Co., Inc of U.S. Autochem Temperature desorption instrument is measured, and specific method is：Weigh 0.2g samples to be tested and load sample cell, be placed in conductance cell heating furnace, He gas For carrier gas (50mL/min), 600 DEG C are warming up to the speed of 20 DEG C/min, purging 60min drives away the miscellaneous of catalyst surface absorption Matter, is then cooled to 100 DEG C, constant temperature 30min, switches to NH₃- He gaseous mixtures (10.02%NH₃+ 89.98%He) absorption 30min, be further continued for sweeping 90min with He air-blowings it is steady to baseline, to be desorbed the ammonia of physical absorption；With 10 DEG C/min heating rates It is warming up to 600 DEG C to be desorbed, keeps 30min, desorption terminates；It is automatic using TCD detector detection gas change of component, instrument Integration obtains total acid content.

The content of the sodium content of catalyst, phosphorus content and carried metal is carried out using GB/T 30905-2014 standard methods Measure.

In each embodiment and comparative example：

Quality × 100% of BTX yields (%)=(quality of BTX in quality-reactant of BTX in product)/reactant

Quality × 100% of quality/reactant of propylene in propene yield (%)=product

The property of raw materials is as follows in embodiment and comparative example：Kaolin (Suzhou China Kaolin Co., Ltd is purchased from, Gu 75 weight % of content), montmorillonite (is purchased from Chaoyang City, Liaoning Province Hong Shi bentonites company, 75 weight % of solid content), Aluminum sol (purchase From Shandong catalyst branch company, alumina content is 22.5 weight %), Ludox (is purchased from Qingdao Marine Chemical Co., Ltd., oxygen 25.5 weight % of SiClx content, pH value 3.0), Beta molecular sieves (are purchased from Shandong catalyst branch company).

Embodiment 1

470.6g Ludox is mixed with 112g kaolin, and it is 26.8 weights to be configured to solid content with decationized Y sieve water Measure % slurries, stirring 2 it is small when after add 96gBeta molecular sieves, is formed solid content for 35 weight % slurries, after continuing stirring Spray drying, then when 500 DEG C of roastings 2 are small, is made spray dried microspheres A1.

Take the spray dried microspheres A1 (butt quality) that 200g is made above, add water be beaten solid content is 10 weight % Slurries, add 15.6g high alkali deflection aluminium acid sodium solution (Na₂O is 290g/L, Al₂O₃For 40g/L, solution density 1.353g/mL), It 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 10 weight % slurries, 6.2g oxalic acid is added in stirring, then adds 54g hydrochloric acid (mass fraction 10%) and 145g fluosilicic acid (concentration 3%) cocurrent, Be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, when 550 DEG C of calcination process 2 are small after, according to the institute of dry basis State the material after calcination process：Ammonium salt：H₂O=1：0.5：5 weight ratio carry out at room temperature ammonium exchange processing 0.5 it is small when after mistake Filter, this exchange process are repeated 4 times, and filter cake is obtained after dry；By filter cake plus water be beaten solid content be 40 weight % slurries, will 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, is then dried It is dry, obtain catalyst sample A when 550 DEG C of calcination process 2 are small, the phosphorus content of catalyst sample A is 3.45 weight %, iron content For 3.48 weight %, other physico-chemical properties are listed in table 1；Catalyst sample A is former after 800 DEG C, 100% vapor aging 14h Material oil ACE evaluating datas are listed in table 1.

Comparative example 1

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 30.1g high alkali deflection aluminium acid sodium solution (Na₂O is 280g/L, Al₂O₃For 40g/L, solution density 1.25g/mL), Be warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing drying, when 550 DEG C of calcination process 2 are small after, according to dry basis Material after the calcination process：Ammonium salt：H₂O=1：0.5：5 weight ratio carry out at room temperature ammonium exchange processing 0.5 it is small when after Filtering, this exchange process are repeated 4 times, and filter cake is obtained after dry；By filter cake plus water be beaten solid content be 40 weight % slurries, By 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, then Drying, catalyst sample A is obtained when 550 DEG C of calcination process 2 are small, the phosphorus content of catalyst sample A is 3.43 weight %, and iron contains Measure and be listed in table 1 for 3.44 weight %, other physico-chemical properties；Catalyst sample DB1 passes through 800 DEG C, 100% vapor aging 14h Afterwards, feedstock oil ACE evaluating datas are listed in table 1.

Comparative example 2

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 6.0g oxalic acid, 55g hydrochloric acid (mass fraction 10%) and 145g fluosilicic acid (concentration are then slowly added dropwise in stirring 3%), be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, when 550 DEG C of calcination process 2 are small after, according to butt weight Material after the calcination process of meter：Ammonium salt：H₂O=1：0.5：It is small that 5 weight ratio carries out ammonium exchange processing 0.5 at room temperature When after filter, this exchange process is repeated 4 times, and filter cake is obtained after dry；By filter cake plus water be beaten solid content is 40 weight % Slurries, by 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, Then to dry, catalyst sample A is obtained when 550 DEG C of calcination process 2 are small, the phosphorus content of catalyst sample A is 3.39 weight %, Iron content is 3.37 weight %, other physico-chemical properties are listed in table 1, catalyst sample DB2 by 800 DEG C, 14h, 100% vapor After aging, feedstock oil ACE evaluating datas are listed in table 1.

Comparative example 3

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 18.7gNaOH (purity 96%), are 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 10 weight % slurries, in stirring add oxalic acid 12.7g, then add 246g hydrochloric acid (mass fractions 10%), be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, when 550 DEG C of calcination process 2 are small after, according to butt weight Material after the calcination process of meter：Ammonium salt：H₂O=1：0.5：It is small that 5 weight ratio carries out ammonium exchange processing 0.5 at room temperature When after filter, this exchange process is repeated 4 times, and filter cake is obtained after dry；By filter cake plus water be beaten solid content is 40 weight % Slurries, by 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, Then to dry, catalyst sample A is obtained when 550 DEG C of calcination process 2 are small, the phosphorus content of catalyst sample A is 3.42 weight %, Iron content is 3.47 weight %, other physico-chemical properties are listed in table 1, and catalyst sample DB3 passes through 800 DEG C, 100% vapor aging After 14h, feedstock oil ACE evaluating datas are listed in table 1.

Comparative example 4

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 13.2gNaOH (purity 96%), are 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 10 weight % slurries, oxalic acid 41.5g is added in stirring, 50 DEG C of constant temperature stirring 1h is warming up to, crosses diafiltration Wash drying, when 550 DEG C of calcination process 2 are small after, according to the material after the calcination process with dry basis：Ammonium salt：H₂O =1：0.5：5 weight ratio carry out at room temperature ammonium exchange processing 0.5 it is small when after filter, this exchange process is repeated 4 times, after dry Obtain filter cake；By filter cake plus water be beaten solid content be 40 weight % slurries, by 12.8gH₃PO₄(concentration 85%) with 17.6gFe(NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, is then dried, small in 550 DEG C of calcination process 2 When obtain catalyst sample A, the phosphorus content of catalyst sample A is 3.44 weight %, and iron content is 3.40 weight %, other materializations Property is listed in table 1, and after 800 DEG C, 100% vapor aging 14h, feedstock oil ACE evaluating datas are listed in catalyst sample DB4 Table 1.

Comparative example 5

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 13.2gKOH (purity 96%), are warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content be 10 The slurries of weight %, add 31.2g oxalic acid, 112g fluosilicic acid (concentration 3%) are then slowly added dropwise, is warming up to 50 DEG C of perseverances in stirring Temperature stirring 1h, filtration washing drying, when 550 DEG C of calcination process 2 are small after, after the calcination process with dry basis Material：Ammonium salt：H₂O=1：0.5：5 weight ratio carry out at room temperature ammonium exchange processing 0.5 it is small when after filter, this is exchanged Journey is repeated 4 times, and filter cake is obtained after dry；By filter cake plus water be beaten solid content be 40 weight % slurries, by 12.8gH₃PO₄ (concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping, is then dried, at 550 DEG C with above-mentioned slurries Calcination process 2 obtains catalyst sample A when small, the phosphorus content of catalyst sample A is 3.45 weight %, and iron content is 3.45 weights % is measured, other physico-chemical properties are listed in table 1, and catalyst sample DB5 is after 800 DEG C, 100% vapor aging 14h, feedstock oil ACE evaluating datas are listed in table 1.

Comparative example 6

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 13.2LiOH (purity 96%), are warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content be 10 The slurries of weight %, add 175g hydrochloric acid (mass fraction 10%), 112g fluosilicic acid (concentration are then slowly added dropwise in stirring 3%), be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, when 550 DEG C of calcination process 2 are small after, according to butt weight Material after the calcination process of meter：Ammonium salt：H₂O=1：0.5：It is small that 5 weight ratio carries out ammonium exchange processing 0.5 at room temperature When after filter, this exchange process is repeated 4 times, and filter cake is obtained after dry；By filter cake plus water be beaten solid content is 40 weight % Slurries, by 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, Then to dry, catalyst sample A is obtained when 550 DEG C of calcination process 2 are small, the phosphorus content of catalyst sample A is 3.42 weight %, Iron content is 3.43 weight %, other physico-chemical properties are listed in table 1, after 800 DEG C, 100% vapor aging 14h, feedstock oil ACE evaluating datas are listed in table 1.

Comparative example 7

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 13.2LiOH (purity 96%), are warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content be 10 The slurries of weight %, are slowly added dropwise 112g fluosilicic acid (concentration 3%) in stirring, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing It is dry, when 550 DEG C of calcination process 2 are small after, according to the material after the calcination process with dry basis：Ammonium salt：H₂O= 1：0.5：5 weight ratio carry out at room temperature ammonium exchange processing 0.5 it is small when after filter, this exchange process is repeated 4 times, it is dry after To filter cake；By filter cake plus water be beaten solid content be 40 weight % slurries, by 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, is then dried, urged when 550 DEG C of calcination process 2 are small The phosphorus content of agent sample A, catalyst sample A are 3.38 weight %, and iron content is 3.47 weight %, other physico-chemical properties are listed in Table 1, after 800 DEG C, 100% vapor aging 14h, feedstock oil ACE evaluating datas are listed in table 1.

Comparative example 8

Spray dried microspheres A1 (butt quality) plus water prepared by 200g embodiments 1 are configured to 10 weight %'s of solid content Slurries, add 13.2LiOH (purity 96%), are warming up to 50 DEG C of constant temperature stirring 0.5h；By filter cake plus water be beaten solid content be 10 The slurries of weight %, add 175g hydrochloric acid (mass fraction 10%) in stirring, be warming up to 50 DEG C of constant temperature stirring 1h, and filtration washing is done It is dry, when 550 DEG C of calcination process 2 are small after, according to the material after the calcination process with dry basis：Ammonium salt：H₂O=1： 0.5：5 weight ratio carry out at room temperature ammonium exchange processing 0.5 it is small when after filter, this exchange process is repeated 4 times, and is obtained after dry Filter cake；By filter cake plus water be beaten solid content be 40 weight % slurries, by 12.8gH₃PO₄(concentration 85%) and 17.6gFe (NO₃)₃·9H₂O is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, is then dried, urged when 550 DEG C of calcination process 2 are small The phosphorus content of agent sample A, catalyst sample A are 3.43 weight %, and iron content is 3.45 weight %, other physico-chemical properties are listed in Table 1, after 800 DEG C, 100% vapor aging 14h, feedstock oil ACE evaluating datas are listed in table 1.

Embodiment 2

266.7g Aluminum sols are mixed with 152g montmorillonites, and it is 23.8 weights to be configured to solid content with decationized Y sieve water Measure % slurries, stirring 1 it is small when after add 126gBeta molecular sieves, is formed solid content for 35 weight % slurries, continue to stir After be spray-dried, then 350 DEG C roasting 2 it is small when, spray dried microspheres B1 is made.

The spray dried microspheres B1 (butt quality) that 200g is made above is taken, adds water to be configured to the slurry of 10 weight % of solid content Liquid, adds 20.5gNaOH (purity 96%), is warming up to 90 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water are beaten Starch solid content be 10 weight % slurries, 25.1g oxalic acid is added in stirring, then by 120g sulfuric acid (mass fraction 10%) and 966.7g fluosilicic acid (concentration 3%) cocurrent adds, and is warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, at 550 DEG C of roastings Manage 2 it is small when after, according to the material after the calcination process with dry basis：Ammonium salt：H₂O=1：0.5：5 weight ratio exists Filtered after when progress ammonium exchange processing 0.5 is small at room temperature, this exchange process is repeated 4 times, and obtains filter cake after dry, filter cake adds water to beat Starch solid content be 40 weight % slurries, by 9.3g (NH₄)₂HPO₄With 29.1gZn (NO₃)₂·6H₂O is dissolved in 90g water, with Above-mentioned slurries are mixed with dipping, and are then dried, when 550 DEG C of calcination process 2 are small, are obtained catalyst sample B, catalyst sample B's Phosphorus content is 4.58 weight %, and Zn content is 8.05 weight %, other physico-chemical properties are listed in table 2, is steamed by 800 DEG C, 100% water After gas aging 14h, feedstock oil ACE evaluating datas are listed in table 2.

Embodiment 3

The spray dried microspheres B1 (butt quality) for taking 200g embodiments 2 to prepare, adds water to be configured to 10 weight % of solid content Slurries, add 33.1gKOH (purity 96%), be 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 10 weight % slurries, in stirring add 34.2g oxalic acid, then by 235g hydrochloric acid (mass fractions 10%) added with 98g fluosilicic acid (concentration 3%) cocurrent, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, in 550 DEG C of roastings After when burning processing 2 is small, according to the material after the calcination process with dry basis：Ammonium salt：H₂O=1：0.5：5 weight Than carry out at room temperature ammonium exchange processing 0.5 it is small when after filter, this exchange process is repeated 4 times, and filter cake is obtained after dry；By filter cake Add water be beaten solid content be 40 weight % slurries, in 19.5gH₃PO₄180g water is added in (concentration 85%), with above-mentioned slurries It is mixed with dipping, then dries, when 550 DEG C of calcination process 2 are small；Sample after P Modification is pressed into solid-liquid weight ratio 5.2:1 ratio Example and the Cu (NO that concentration is 6%₃)₂Solution exchanged at 80-90 DEG C 2 it is small when, filtering, then exchanges several times, until reaching target Amount, through 550 DEG C of calcination process 2 it is small when, obtain catalyst sample C, the phosphorus content of catalyst sample C is 5.53 weight %, and copper contains Measure and be listed in table 2 for 1.59 weight %, other physico-chemical properties, catalyst sample C after 800 DEG C, 100% vapor aging 14h, Feedstock oil ACE evaluating datas are listed in table 2.

Embodiment 4

The spray dried microspheres B1 (butt quality) for taking 200g embodiments 2 to prepare, adds water to be configured to 10 weight % of solid content Slurries, add 21.2gNaOH (purity 96%), be 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 10 weight % slurries, in stirring add 5.6g citric acids, then by 247g hydrochloric acid (mass fractions 10%) added with 145g fluosilicic acid (concentration 3%) cocurrent, be warming up to 50 DEG C of constant temperature stirring 1h, filtration washing drying, at 550 DEG C After when calcination process 2 is small, according to the material after the calcination process with dry basis：Ammonium salt：H₂O=1：0.5：5 weight Amount than at room temperature carry out ammonium exchange processing 0.5 it is small when after filter, this exchange process is repeated 4 times, drying after obtain filter cake；Will filter Cake add water be beaten solid content be 40 weight % slurries, by 1.95gH₃PO₄(concentration 85%) and 35.4gCo (NO₃)·6H₂O It is dissolved in 90g water, is mixed with dipping with above-mentioned slurries, then dries, catalyst sample D is obtained when 550 DEG C of calcination process 2 are small, The phosphorus content of catalyst sample D is 0.52 weight %, and cobalt content is 9.10 weight %, other physico-chemical properties are listed in table 2, catalyst For sample D after 800 DEG C, 100% vapor aging 14h, feedstock oil ACE evaluating datas are listed in table 2.

Comparative example 9

In this comparative example basic process according to embodiment 1 method, difference lies in without alkali process, compound acid treatment, P Modification processing and carried metal processing, gained sample are contrast sample I, its physico-chemical property is listed in table 2, feedstock oil ACE evaluations Data are listed in table 2.

Comparative example 10

Basic process is according to the method for embodiment 1 in this comparative example, and difference lies in without P Modification processing and gold-supported Category processing, gained sample are contrast sample II, its physico-chemical property is listed in table 2, and feedstock oil ACE evaluating datas are listed in table 2.

Comparative example 11

In this comparative example basic process according to embodiment 1 method, difference lies in being handled without P Modification, gained sample To contrast sample III, its physico-chemical property is listed in table 2, and feedstock oil ACE evaluating datas are listed in table 2.

Comparative example 12

In this comparative example basic process according to embodiment 1 method, difference lies in being handled without carried metal, gained sample Product are contrast sample IV, its physico-chemical property is listed in table 2, and feedstock oil ACE evaluating datas are listed in table 2.

Compared to only with alkali process (DB1) or only with fluosilicic acid, organic it can be seen from data in Tables 1 and 2 The compound acid treatment (DB2) of acid and inorganic acid composition uses single organic acid oxalic acid treatment (DB4) or uses single inorganic Hydrochlorate acid treatment (DB8) uses single fluosilicic acid dealumination treatment (DB7) or uses organic acid oxalic acid and inorganic acid hydrochloric acid two Kind acid treatment (DB3) is using fluosilicic acid composite organic acid oxalic acid treatment (DB5) or sour using fluosilicic acid composite inorganic hydrochlorate Handle the catalytic cracking catalyst obtained by (DB6), the disclosure using first by conventional Beta system with molecular sieve for preparing into passing through after catalyst again The method of soda acid coupling processing carries out modulation to the pore passage structure of molecular sieve, it is ensured that it is newly-generated it is mesoporous be not plugged, can So that total specific surface area of catalyst is 240-350m²/ g, the ratio that mesoporous Bronsted acid amount accounts for total acid content is 20-70%, mesoporous Volume is 0.14-0.35ml/g, and the ratio that mesopore volume accounts for total pore volume is 35-60%.Prepared using disclosed method Catalyst is used in naphtha catalytic cracking, and BTX yields can be improved to 5-150%, and propene yield improves 1-170%, in addition, The selectivity of liquefied gas in product can also be improved, reduces the selectivity of diesel oil and coke.

Table 1

Table 2

Table 3

Claims

1. a kind of catalytic cracking catalyst, on the basis of the butt weight of the catalyst, which is included with butt weight Count the BEA structure molecular screens of 24-75 weight %, with the natural clay of dry basis 5-65 weight %, the 10-60 in terms of oxide The inorganic oxide binder of weight %, with P₂O₅Count the phosphorus additive of 0.1-15 weight %, and the 0.1- in terms of the oxide of metal The metallic addition of 15 weight %, the ratio that the mesoporous Bronsted acid amount of the catalyst accounts for total acid content is 20-70%.

2. catalyst according to claim 1, wherein, with P₂O₅Count and on the basis of the butt weight of the catalyst, institute The content for stating phosphorus additive is 0.5-6.5 weight %, is counted using the oxide of metal and using the butt weight of the catalyst as base Standard, the content of the metallic addition is 0.5-10 weight %.

3. catalyst according to claim 1, wherein, total specific surface area of the catalyst is 240-350m²/ g, it is mesoporous The ratio that Bronsted acid amount accounts for total acid content is 25-50%.

4. catalyst according to claim 1, wherein, the mesopore volume of the catalyst is 0.14-0.35ml/g, mesoporous The ratio that volume accounts for total pore volume is 35-60%.

5. catalyst according to claim 1, wherein, the natural clay is de- selected from kaolin, halloysite, illiteracy At least one of soil, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite；The inorganic oxygen Compound binding agent is selected from least one of silica, aluminium oxide, zirconium oxide, titanium oxide and amorphous silica-alumina.

6. catalyst according to claim 1, wherein, the metal is in iron, cobalt, nickel, copper, manganese, zinc, tin and titanium At least one.

7. according to the catalyst described in any one in claim 1-4, wherein, it is total specific surface area of the catalyst, mesoporous Volume and total pore volume are measured using N2 adsorption BET specific surface area method；The mesoporous Bronsted acid amount uses bis- uncles of 2,6- Butyl-pyridinium is adsorbed infrared acid process and is measured, and the mesoporous Bronsted acid refers to that kinetic diameter is2,6- bis- The Bronsted acid that tert .-butylpyridine molecule can touch；The total acid content uses NH₃- TPD methods measure.

A kind of 8. method for preparing catalytic cracking catalyst, it is characterised in that this method comprises the following steps：

A, BEA structure molecular screens, natural clay, inorganic oxide binder presoma and water are mixed and are beaten uniformly, then Gained slurries are spray-dried, obtain spray dried microspheres, wherein, on the basis of total butt weight of spray dried microspheres, institute Stating spray dried microspheres is included with the BEA structure molecular screens of dry basis 25-75 weight %, with dry basis 5-65 weights Measure the natural clay of %, and the inorganic oxide binder presoma of the weight of the 10-60 in terms of oxide %；

B, the spray dried microspheres obtained in step a are subjected to alkali process, and after being filtered and being washed, obtain alkali process Material afterwards；

C, the material after the alkali process that will be obtained in step b is in the Compound-acid being made of fluosilicic acid, organic acid and inorganic acid Acid treatment for composite in solution, and after being filtered and being washed, obtain the material after compound acid treatment；

D, the material after the compound acid treatment obtained in step c is subjected to P Modification processing, carried metal processing and first After calcination process, catalytic cracking catalyst is obtained, wherein, with P₂O₅Count and on the basis of the butt weight of the catalyst, phosphorus adds The content for adding agent is 0.1-15 weight %, is counted by the oxide of metal and on the basis of the butt weight of the catalyst, metal The content of additive is 0.1-15 weight %；

Wherein, the ratio that the mesoporous Bronsted acid amount of the catalyst accounts for total acid content is 20-70%.

9. according to the method described in claim 8, wherein, total specific surface area of the catalyst is 240-350m²/ g, mesoporous matter The ratio that sub- acid amount accounts for total acid content is 25-50%.

10. according to the method described in claim 8, wherein, the mesopore volume of the catalyst is 0.14-0.35ml/g, mesoporous The ratio that volume accounts for total pore volume is 35-60%.

11. according to the method described in any one in claim 8-10, wherein, it is total specific surface area of the catalyst, mesoporous Volume and total pore volume are measured using N2 adsorption BET specific surface area method；The mesoporous Bronsted acid amount uses bis- uncles of 2,6- Butyl-pyridinium is adsorbed infrared acid process and is measured, and the mesoporous Bronsted acid refers to that kinetic diameter is2,6- bis- The Bronsted acid that tert .-butylpyridine molecule can touch；The total acid content uses NH₃- TPD methods measure.

12. according to the method described in claim 8, wherein, the natural clay in step a is high selected from kaolin, more water At least one of ridge soil, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite； The inorganic oxide binder presoma is selected from Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorous aluminium At least one of colloidal sol.

13. according to the method described in claim 8, wherein, the alkali process in step b includes：The spray drying is micro- Ball is mixed with alkaline solution, and the alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonia At least one of water and high alkali deflection aluminium acid sodium solution.

14. according to the method for claim 13, wherein, the condition of the mixing includes：With the spray of dry basis The weight ratio of alkali in mist dry microspheres and alkaline solution is 1：(0.01-0.35)；Wherein, the alkali in the sodium hydroxide solution Weight in terms of the weight of sodium hydroxide, the weight of the alkali in the potassium hydroxide solution is described in terms of the weight of potassium hydroxide The weight of alkali in lithium hydroxide solution is in terms of the weight of lithium hydroxide, and the weight of the alkali in the ammonium hydroxide is with the weight of a hydration ammonia Gauge, the weight of the alkali in the high alkali deflection aluminium acid sodium solution is in terms of the weight of sodium oxide molybdena.

15. the method according to claim 11, wherein, with the spray dried microspheres and alkaline solution of dry basis In alkali weight ratio be 1：(0.05-0.25).

16. according to the method described in claim 8, wherein, the organic acid in step c is selected from ethylenediamine tetra-acetic acid, grass At least one of acid, citric acid and sulfosalicylic acid, the inorganic acid are at least one in hydrochloric acid, sulfuric acid and nitric acid Kind.

17. according to the method described in claim 8, wherein, the condition of the compound acid treatment in step c is：With dry basis The weight ratio of material, fluosilicic acid, inorganic acid and organic acid after the alkali process of gauge is 1：(0.01-0.45)：(0.01- 0.45)：(0.01-0.55).

18. according to the method for claim 17, wherein, the condition of the compound acid treatment in step c is：With dry basis The weight ratio of material, fluosilicic acid, inorganic acid and organic acid after the alkali process of gauge is 1：(0.05-0.3)：(0.1- 0.3)：(0.1-0.3).

19. method according to claim 8, wherein, this method further includes：After the compound acid treatment obtained in step c Material carry out the second calcination process, the material after the second calcination process is obtained, then to the thing after second calcination process Material carries out ammonium exchange processing, obtains the material after ammonium exchange processing, then carries out the P Modification processing, carried metal processing again With the first calcination process.

20. method according to claim 19, wherein, the condition of second calcination process includes：The gas of second calcination process Atmosphere is air atmosphere or nitrogen atmosphere or steam atmosphere；The temperature of roasting is 400-800 DEG C, and the time of roasting is small for 0.5-8 When.

21. according to the method for claim 19, wherein, the ammonium exchanges processing and causes, is urged in terms of sodium oxide molybdena and with described On the basis of the total butt weight for changing catalyst for cracking, the sodium content of the catalytic cracking catalyst is less than 0.15 weight %；It is described Ammonium exchange processing includes：Material after second calcination process is mixed with ammonium salt, the ammonium salt is selected from ammonium chloride, sulfuric acid At least one of ammonium, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate and ammonium nitrate.

22. according to the method described in claim 8, wherein, the P Modification processing in step d includes：By phosphorus-containing compound Molecular sieve is impregnated and/or ion exchange, the phosphorus-containing compound be selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and At least one of ammonium phosphate.

23. according to the method described in claim 8, wherein, the carried metal processing in step d includes：By dipping side Method loads to the carried metal of the compound containing carried metal on catalyst, the carried metal be selected from iron, cobalt, At least one of nickel, copper, manganese, zinc, tin and titanium, the compound containing carried metal are the water containing the carried metal Soluble.

24. according to the method for claim 23, wherein, the compound containing carried metal is selected from containing described negative Carry at least one of sulfate, nitrate and chlorate of metal.

25. method according to claim 8, wherein, the condition of first calcination process in step d includes：First roasting The atmosphere of processing is air atmosphere or nitrogen atmosphere or steam atmosphere；The temperature of roasting is 400-800 DEG C, and the time of roasting is When 0.5-8 is small.

26. a kind of catalytic cracking catalyst, it is characterised in that the catalytic cracking catalyst is by any one in claim 8-25 What the method described in was prepared.

A kind of 27. method of petroleum hydrocarbon catalytic pyrolysis, it is characterised in that this method includes：Under conditions of catalytic pyrolysis, make stone Petroleum hydrocarbon carries out haptoreaction with the catalytic cracking catalyst described in any one in claim 1-7 and 26.