CN107971006B

CN107971006B - A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof

Info

Publication number: CN107971006B
Application number: CN201610921992.0A
Authority: CN
Inventors: 任飞; 朱玉霞; 田辉平; 刘倩倩; 欧阳颖; 罗一斌
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: 2019-10-25
Anticipated expiration: 2036-10-21
Also published as: CN107971006A

Abstract

This disclosure relates to a kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof, on the basis of the dry weight of the auxiliary agent, the auxiliary agent includes the phosphorous and carried metal IMF structure molecular screen with dry basis 10-75 weight %, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, other inorganic binders of the weight of the 1-30 in terms of oxide %, with the metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of the second clay of dry basis 0-60 weight %, and the weight of the 0.5-15 in terms of oxide %.The auxiliary agent that the disclosure is provided is used for catalytic cracking process, can effectively improve propene yield and Propylene Selectivity.

Description

A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof

Technical field

This disclosure relates to a kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof.

Background technique

For a long time, ethylene, propylene and butylene are that the basic organic chemical industry of synthetic resin, synthetic fibers and synthetic rubber is former Material, wherein propylene is be only second to ethylene a kind of for manufacturing the important source material of petroleum chemicals.The maximum of domestic and international propylene at present Source is the Main By product of thermal cracking production ethylene, and the second largest source of propylene provides about nearly all from FCC apparatus 30% demand, in the U.S., FCC apparatus then provides petroleum chemicals to about half demand of propylene.

Due to increasing rapidly to polyacrylic demand, make the required propylene of petrochemical industry faster than ethylene requirements, and The construction of ethylene plant is limited to the demand of ethylene, therefore a large amount of volume increase FCC propylene will be used for the increase of meet demand.From previous generation It has recorded since the eighties, the catalyst of the ZSM-5 containing shape-selective molecular sieve starts to put into industrial application on FCC apparatus, has reached volume increase C₃ ⁼Purpose, but the greatest weakness of this kind of ZSM-5 molecular sieve is that activity stability is poor, in the periodic regeneration of FCC apparatus harshness Under the conditions of easy in inactivation.

IM-5 molecular sieve is a kind of IMF structure molecular screen, is synthesized for the first time by Benazzi in 1998.2007 by Baerlocher et al. completes the parsing work of structure.The molecular sieve is two-dimentional ten-ring cellular structure, channel diameter with ZSM-5 molecular sieve is similar, and there is also a limited ducts on third dimension direction.Since it has and ZSM-5 molecular sieve phase Close cellular structure, while there is higher acid amount and better hydrothermal stability, therefore show in many catalysis reaction Characteristic.Corma et al. has carried out a series of researchs to the catalytic performance of IM-5 molecular sieve, finds it in terms of alkane cracking capability Higher than ZSM-5 molecular sieve.

Although IM-5 molecular sieve can alkane cracking capability with higher, it is identical as other ten-ring molecular sieves, by Narrow in its cellular structure, biggish reactant molecule such as polycyclic hydro carbons are difficult to enter in crystal duct and are reacted, and reduce The effective affecting acreage of molecular sieve reduces the reactivity of molecular sieve；On the other hand, isoparaffin and aromatic hydrocarbons etc. are biggish Product molecule is also not easy to diffuse out inside molecular sieve pore passage, in turn so as to cause secondary responses such as excessive hydrogen migration, cokings Molecular sieve inactivation, reaction selectivity is caused to reduce.In the cracking reaction for being divided into raw material with macromolecular recombination, IM-5 molecular sieve pores The defect of road hole stenostomia necessarily makes problem above more prominent.

Summary of the invention

Purpose of this disclosure is to provide assistant for calalytic cracking of a kind of propylene enhancing and preparation method thereof, and the disclosure is provided Auxiliary agent be used for catalytic cracking process, propene yield and Propylene Selectivity can be effectively improved.

To achieve the goals above, the disclosure provides a kind of assistant for calalytic cracking of propylene enhancing, with the dry of the auxiliary agent On the basis of base weight amount, which includes the phosphorous and carried metal IMF structure molecular screen with dry basis 10-75 weight %, With the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, other inorganic binders of the weight of the 1-30 in terms of oxide %, With the second clay of dry basis 0-60 weight %, and the weight of the 0.5-15 in terms of oxide % selected from VIII race's metal and manganese, The metallic addition of at least one of zinc, gallium；Wherein, the phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or glues containing first The phosphorus aluminium inorganic binder of soil, it is described to contain first on the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay The phosphorus aluminium inorganic binder of clay includes with Al₂O₃Count 15-40 weight % aluminium component, with P₂O₅Count the phosphorus component of 45-80 weight % And it is greater than 0 with dry basis and is no more than the first clay of 40 weight %, and its P/Al weight ratio is 1.0-6.0, pH value For 1-3.5, solid content is 15-60 weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85；Wherein, D= Al (S)/Al (C), Al (S) are indicated using the inside H in crystal face edge of the zeolite crystal of TEM-EDS method measurement apart from interior any Greater than the aluminium content in 100 square nanometers regions, Al (C) indicates crystal face described in the zeolite crystal using the measurement of TEM-EDS method The outside H of geometric center apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is the crystal face edge Certain point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 The ratio of body %, the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers are greater than 85 body %；The molecular sieve it is strong The ratio that sour amount accounts for total acid content is 50-80%, and the ratio between B acid acid amount and L acid acid amount are 7-30；With P₂O₅It counts and with molecular sieve On the basis of dry weight, the phosphorus content of the molecular sieve is 0.1-15 weight %；In terms of the oxide of the carried metal and with institute On the basis of the dry weight for stating molecular sieve, carried metal content is 0.1-5 weight % in the molecular sieve.

Preferably, the Al distribution parameter D of the molecular sieve meets: 0.65≤D≤0.82；The mesopore volume of the molecular sieve The ratio for accounting for total pore volume is 57-70 body %, and the ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is big In 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-70%, and the ratio between B acid acid amount and L acid acid amount are 8- 25；With P₂O₅It counts and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-13 weight %；With the load The oxide meter of metal and on the basis of the dry weight of the molecular sieve, carried metal content is 0.5-3 in the molecular sieve Weight %.

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

Preferably, first clay is selected from kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatom At least one of soil；Second clay is de- selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, illiteracy At least one of stone and rectorite；Other inorganic matter binders be selected from boehmite, Aluminum sol, silicon-aluminum sol and At least one of waterglass.

Preferably, the metallic addition introduces the auxiliary agent in the form of metallic compound, and the metallic compound is Selected from least one of oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound.

Preferably, on the basis of the dry weight of the auxiliary agent, the auxiliary agent also contains with P₂O₅Meter is no more than 5 weight % Phosphorus additive.

Preferably, the auxiliary agent includes the phosphorous and load of the phosphorus aluminium inorganic binder of 8-25 weight %, 20-60 weight % Metal IMF structure molecular screen, the second clay of 10-45 weight %, other inorganic binders of 5-25 weight %, 1.0-10 weight Measure the metallic addition of % and the phosphorus additive of 0-3 weight %.

The disclosure also provides a kind of preparation method of the assistant for calalytic cracking of propylene enhancing, this method comprises: by phosphorous and Carried metal IMF structure molecular screen, phosphorus aluminium inorganic binder and the mixing of other inorganic binders, add or are added without the second clay, Mashing, spray drying；Wherein, metallic addition is introduced, phosphorus additive is introduced or do not introduce；The total dry of raw material is prepared with auxiliary agent On the basis of base weight amount, the raw material for preparing of the auxiliary agent includes with the phosphorous and carried metal IMF of dry basis 10-75 weight % Structure molecular screen, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, the weight of the 1-30 in terms of oxide %'s is other Inorganic binder, with the second clay of dry basis 0-60 weight %, the weight of the 0.5-15 in terms of oxide %'s is selected from VIII race The metallic addition of at least one of metal and manganese, zinc, gallium, and including or do not include with P₂O₅Meter is no more than 5 weight %'s Phosphorus additive；Wherein, the phosphorus aluminium inorganic binder be phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, with On the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay, the phosphorus aluminium inorganic binder packet for containing the first clay It includes with Al₂O₃Count 15-40 weight % aluminium component, with P₂O₅It counts the phosphorus component of 45-80 weight % and is greater than 0 with dry basis And it is no more than the first clay of 40 weight %, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content 15-60 Weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) are indicated The inside H in crystal face edge using the zeolite crystal of TEM-EDS method measurement is arbitrarily greater than 100 square nanometers regions apart from interior Aluminium content, Al (C) are indicated in the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method Any aluminium content for being greater than 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometrical center to center From 10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, and aperture is 2 nanometers -20 nanometers The ratio of the total mesopore volume of mesopore volume Zhan is greater than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50- The ratio between 80%, B acid acid amount and L acid acid amount are 7-30；With P₂O₅Count and on the basis of the dry weight of molecular sieve, the molecular sieve Phosphorus content be 0.1-15 weight %；It is counted by the oxide of the carried metal and on the basis of the dry weight of the molecular sieve, Carried metal content is 0.1-5 weight % in the molecular sieve.

Preferably, the phosphorous and carried metal IMF structure molecular screen preparation step includes: a, by sodium form IMF structure Molecular sieve carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；B, gained desiliconization molecular sieve in step a is subjected to ammonium friendship Processing is changed, ammonium exchange molecular sieve is obtained；Wherein, by sodium oxide molybdena count and by ammonium exchange molecular sieve total dry weight on the basis of, institute State the sodium content % heavy less than 0.2 of ammonium exchange molecular sieve；C, by gained ammonium exchange molecular sieve in step b by fluosilicic acid, organic Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of acid and inorganic acid composition, and after being filtered and washed, obtains dealuminzation point Son sieve；D, after dealuminzation molecular sieve obtained in step c being carried out P Modification processing, carried metal modification and calcination process, Obtain described phosphorous and carried metal IMF structure molecular screen.

Preferably, the preparation step of sodium form IMF structure molecular screen described in step a includes: and will use to have amine method crystallization institute After IMF structure molecular screen slurries are filtered and washed, obtain washing molecular sieve；Wherein, it is washed in terms of sodium oxide molybdena and with described Sodium content % heavy less than 3.0 on the basis of the total dry weight for washing molecular sieve, in the washing molecular sieve；By the washing molecule Sieve is dried and after air roasting, obtains the sodium form IMF structure molecular screen.

Preferably, aqueous slkali described in step a is in sodium hydrate aqueous solution, potassium hydroxide aqueous solution and ammonium hydroxide It is at least one.

Preferably, desiliconization described in step a processing condition include: with the sodium form IMF structure molecular screen of dry basis, The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1:(0.1-2): the temperature of (5-20), the desiliconization processing are room temperature To 100 DEG C, the time is 0.2-4 hours.

Preferably, desiliconization described in step a processing condition include: with the sodium form IMF structure molecular screen of dry basis, The weight ratio of the water in alkali and aqueous slkali in aqueous slkali is 1:(0.2-1): (5-20).

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

Preferably, the condition of dealumination treatment described in step c includes: with the ammonium of dry basis exchange molecular sieve, organic The weight ratio of acid, inorganic acid and fluosilicic acid is 1:(0.01-0.3): (0.01-0.3): (0.01-0.3)；The dealumination treatment Temperature be 25-100 DEG C, the time be 0.5-6 hours.

Preferably, the condition of dealumination treatment described in step c includes: with the ammonium of dry basis exchange molecular sieve, organic The weight ratio of acid, inorganic acid and fluosilicic acid is 1:(0.02-0.2): (0.015-0.2): (0.015-0.2).

Preferably, the processing of P Modification described in step d includes: that will be selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid At least one of ammonium phosphorus-containing compound carries out dipping and/or ion exchange to molecular sieve.

Preferably, carried metal modification described in step d include: will containing selected from iron, cobalt, nickel, copper, manganese, zinc, The carried metal is loaded to the molecular sieve by dipping method by the compound of at least one of tin, bismuth and gallium carried metal On.

Preferably, it is air atmosphere or vapor that the condition of calcination process described in step d, which includes: the atmosphere of calcination process, Atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.

Preferably, the preparation step of the phosphorus aluminium inorganic binder for containing the first clay includes: (1), by alumina source, One clay and water mashing are dispersed into the slurries that solid content is 8-45 weight %；The alumina source is can be by the hydrogen-oxygen of sour peptization Change aluminium and/or aluminium oxide, with the first clay of dry basis and with Al₂O₃The weight ratio of the alumina source of meter is (to be greater than 0- 40):(15-40)；(2), stirring is lower is added concentrated phosphoric acid according to the weight ratio of P/Al=1-6 into the slurries that step (1) obtains； (3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.

The assistant for calalytic cracking that the disclosure provides has preferable Catalytic Cracking Performance, urges with after host agent blending for hydrocarbon ils Change cracking reaction, propene yield and Propylene Selectivity can be effectively improved.

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 assistant for calalytic cracking of propylene enhancing, and on the basis of the dry weight of the auxiliary agent, this is helped Agent includes the phosphorous and carried metal IMF structure molecular screen with dry basis 10-75 weight %, with dry basis 3-40 weight Measure the phosphorus aluminium inorganic binder of %, other inorganic binders of the weight of the 1-30 in terms of oxide %, with dry basis 0-60 weight Measure the second clay of %, and the weight of the 0.5-15 in terms of oxide % selected from least one of VIII race's metal and manganese, zinc, gallium Metallic addition；Wherein, the phosphorus aluminium inorganic binder be phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, On the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay, the phosphorus aluminium inorganic binder for containing the first clay Including with Al₂O₃Count 15-40 weight % aluminium component, with P₂O₅It counts the phosphorus component of 45-80 weight % and is greater than with dry basis 0 and be no more than 40 weight % the first clay, and its P/Al weight ratio be 1.0-6.0, pH value 1-3.5, solid content 15-60 Weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) are indicated The inside H in crystal face edge using the zeolite crystal of TEM-EDS method measurement is arbitrarily greater than 100 square nanometers regions apart from interior Aluminium content, Al (C) are indicated in the outside H distance of the geometric center of crystal face described in the zeolite crystal using the measurement of TEM-EDS method Any aluminium content for being greater than 100 square nanometers regions, wherein the H is that the crystal face edge point arrives the crystal face geometrical center to center From 10%；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, and aperture is 2 nanometers -20 nanometers The ratio of the total mesopore volume of mesopore volume Zhan is greater than 85 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50- The ratio between 80%, B acid acid amount and L acid acid amount are 7-30；With P₂O₅Count and on the basis of the dry weight of molecular sieve, the molecular sieve Phosphorus content be 0.1-15 weight %；It is counted by the oxide of the carried metal and on the basis of the dry weight of the molecular sieve, Carried metal content is 0.1-5 weight % in the molecular sieve.Preferably, the Al distribution parameter D of the molecular sieve meets: 0.65≤ D≤0.82；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 57-70 body %, and aperture is 2 nanometers -20 nanometers The ratio of the total mesopore volume of mesopore volume Zhan is greater than 90 body %；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55- The ratio between 70%, B acid acid amount and L acid acid amount are 8-25；With P₂O₅Count and on the basis of the dry weight of molecular sieve, the molecular sieve Phosphorus content be 1-13 weight %；It is counted by the oxide of the carried metal and on the basis of the dry weight of the molecular sieve, institute Stating carried metal content in molecular sieve is 0.5-3 weight %.

According to the disclosure, the phosphorus aluminium inorganic binder is phosphorus aluminium inorganic binder and/or phosphorus aluminium glue containing the first clay.

A kind of specific embodiment, on the basis of the dry weight of the phosphorus aluminium inorganic binder, the phosphorus aluminium is inorganic Binder includes with Al₂O₃Count 15-40 weight % aluminium component, with P₂O₅Count the phosphorus component of 45-80 weight % and with dry weight The first clay of 0-40 weight % is counted, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight Measure %；For example including with Al₂O₃Count 15-40 weight % aluminium component, with P₂O₅Count the phosphorus component of 45-80 weight % and with butt The first clay of poidometer 1-40 weight %；It preferably comprises with Al₂O₃The aluminium component of 15-35 weight % is counted, with P₂O₅Count 50-75 The phosphorus component of weight % and with the first clay of dry basis 8-35 weight %, P/Al weight ratio is preferably 1.2-6.0, More preferably 2.0-5.0, pH value are preferably 1.5-3.0.

Another specific embodiment, on the basis of the dry weight of the phosphorus aluminium inorganic binder, the phosphorus aluminium without Machine binder includes with Al₂O₃Count 20-40 weight % aluminium component and with P₂O₅Count the phosphorus component of 60-80 weight %.

IMF structure is the topological structure of molecular sieve, such as IM-5 molecular sieve has IMF structure.

According to the disclosure, the carried metal refers to the metal loaded on molecular sieve by mode of loading, does not include aluminium And the alkali metal such as sodium, potassium, may include at least one of selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium, can also be with Including other metals, the disclosure is simultaneously not limited.

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, for example, conventional rectangular bulk IM-5 molecular sieve is long Point of intersection of the geometric center of rectangular crystal face in opposed apexes line.The crystal face is a face of regular crystal grain, it is described to Interior and outwardly direction refers both to the direction inwardly or outwardly on the crystal face.

According to the disclosure, the mesopore volume of the molecular sieve accounts for the ratio of total pore volume and aperture is 2 nanometers -20 nanometers The ratio of the total mesopore volume of mesopore volume Zhan can be measured using N2 adsorption BET specific surface area method, for example, the disclosure can To be measured using GB/T5816-1995 standard method, the mesopore volume refers generally to aperture and receives greater than 2 nanometers less than 100 The pore volume of rice；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content can use NH₃- TPD method measures, described The acid site of strong acid can be NH₃Desorption temperature be greater than 300 DEG C corresponding to acid site；The ratio between the B acid acid amount and L acid acid amount It can be measured using the infrared acid process of pyridine adsorption.

According to the disclosure, metallic addition is added in pulping process, can be the gold in preparing molding auxiliary agent The form for belonging to compound introduces, and is for example, selected from oxide, hydroxide, chloride, nitrate, sulfate, phosphate and has In at least one of machine compound, preferably autoxidisable substance, orthophosphates, phosphite, subphosphate and acid phosphate One or more forms introduce or exist.

According to the disclosure, clay is well known to those skilled in the art, first clay can for selected from kaolin, At least one of sepiolite, attapulgite, rectorite, montmorillonite and diatomite preferably include rectorite, more preferably tired support Soil；Second clay can be for selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatom At least one of soil, galapectite, saponite, boron-moisten soil and hydrotalcite preferably are selected from kaolin, metakaolin, diatomite, Hai Pao At least one of stone, attapulgite, montmorillonite and rectorite；Other inorganic binders can be selected from addition to the phosphorus aluminium glue With the inorganic oxide binder for being customarily used in assistant for calalytic cracking or catalyst binder component other than phosphorus aluminium inorganic binder One of or it is a variety of, preferably be selected from least one of boehmite, Aluminum sol, silicon-aluminum sol and waterglass, more preferably from At least one of boehmite and Aluminum sol.

According to the disclosure, the phosphorus aluminium inorganic binder for containing the first clay is preferably comprised with Al₂O₃Count 15-35 weight % Aluminium component, with P₂O₅Count the phosphorus component of 50-75 weight % and with the first clay of dry basis 8-35 weight %, P/ Al weight ratio is preferably 1.2-6.0, more preferably 2.0-5.0, and pH value is preferably 1.0-3.5.

According to the disclosure, on the basis of the dry weight of the auxiliary agent, the auxiliary agent can also be containing with P₂O₅Meter is no more than The phosphorus additive of 5 weight %.The phosphorus additive can be selected from the compound of phosphorus, inorganic compound for example including phosphorus and have One of machine compound is a variety of, can be soluble easily in water, is also possible to be insoluble in water or phosphorus compound not soluble in water, Such as oxide selected from phosphorus, phosphoric acid, orthophosphates, phosphite, hypophosphites, subphosphate, acid phosphate and One of phosphorous organic compound is a variety of.Preferred phosphorus compound is phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen One of diammonium and aluminum phosphate are a variety of.In obtained auxiliary agent, phosphorus additive is with the phosphorus compound (oxide of such as phosphorus, just Phosphate, phosphite, subphosphate and acid phosphate) form exist.The phosphorus additive can reside in auxiliary agent Any position that may be present such as can reside in inside the duct of zeolite, the surface of zeolite, can reside in host material It in (material i.e. in auxiliary agent in addition to molecular sieve), can also exist simultaneously inside the duct of zeolite, the surface of zeolite and institute It states in host material.Do not include the phosphorus in molecular sieve in the content of phosphorus additive, does not include that the phosphorus aluminium inorganic binder draws yet The phosphorus entered.

According to the disclosure, the auxiliary agent preferably includes the phosphorus aluminium inorganic binder of 8-25 weight %, 20-60 weight % contains Phosphorus and carried metal IMF structure molecular screen, the second clay of 10-45 weight %, 5-25 weight % other inorganic binders, The metallic addition of 1.0-10 weight % and the phosphorus additive of 0-3 weight %.

The disclosure also provides a kind of preparation method of the assistant for calalytic cracking of propylene enhancing, this method comprises:

Phosphorous and carried metal IMF structure molecular screen, phosphorus aluminium inorganic binder and other inorganic binders are mixed, add or It is added without the second clay, is beaten, spray drying；Wherein, metallic addition is introduced, phosphorus additive is introduced or do not introduce；With auxiliary agent The total dry weight for preparing raw material on the basis of, the raw material for preparing of the auxiliary agent includes with dry basis 10-75 weight % Phosphorous and carried metal IMF structure molecular screen, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, in terms of oxide Other inorganic binders of 1-30 weight %, with the second clay of dry basis 0-60 weight %, the 0.5-15 in terms of oxide The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of weight %, and including or do not include with P₂O₅ Meter is no more than the phosphorus additive of 5 weight %；Wherein, the phosphorus aluminium inorganic binder is for phosphorus aluminium glue and/or containing the first clay Phosphorus aluminium inorganic binder, it is described to contain the first clay on the basis of the phosphorus aluminium inorganic binder dry weight for containing the first clay Phosphorus aluminium inorganic binder include with Al₂O₃Count 15-40 weight % aluminium component, with P₂O₅Count 45-80 weight % phosphorus component and It is greater than 0 with dry basis and is no more than the first clay of 40 weight %, and its P/Al weight ratio is 1.0-6.0, pH value 1- 3.5, solid content is 15-60 weight %；The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85；Wherein, D=Al (S)/Al (C), Al (S) are indicated using the inside H in crystal face edge of the zeolite crystal of TEM-EDS method measurement apart from interior arbitrarily large Aluminium content in 100 square nanometers regions, Al (C) indicate crystal face described in the zeolite crystal using the measurement of TEM-EDS method The outside H of geometric center is apart from interior any aluminium content for being greater than 100 square nanometers regions, wherein the H is the crystal face edge Point arrives the 10% of the crystal face geometric center distance；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 50-80 body %, The ratio for the total mesopore volume of mesopore volume Zhan that aperture is 2 nanometers -20 nanometers is greater than 85 body %；The strong acid acid amount of the molecular sieve The ratio for accounting for total acid content is 50-80%, and the ratio between B acid acid amount and L acid acid amount are 7-30；With P₂O₅It counts and with the dry basis of molecular sieve On the basis of amount, the phosphorus content of the molecular sieve is 0.1-15 weight %；In terms of the oxide of the carried metal and with the molecule On the basis of the dry weight of sieve, carried metal content is 0.1-5 weight % in the molecular sieve.

According to the disclosure, the phosphorous and carried metal IMF structure molecular screen preparation step may include: a, by sodium form IMF structure molecular screen carries out desiliconization processing in aqueous slkali, obtains desiliconization molecular sieve；B, by gained desiliconization molecular sieve in step a Ammonium exchange is carried out, ammonium exchange molecular sieve is obtained；Wherein, it is counted using sodium oxide molybdena and total dry weight of molecular sieve is exchanged as base using ammonium Standard, the sodium content % heavy less than 0.2 of the ammonium exchange molecular sieve；C, by step b gained ammonium exchange molecular sieve by fluosilicic acid, Dealumination treatment is carried out in the Compound-acid dealuminzation agent solution of organic acid and inorganic acid composition, and after being filtered and washed, is taken off Aluminum molecular screen；D, dealuminzation molecular sieve obtained in step c is subjected to P Modification processing, carried metal modification and calcination process Afterwards, described phosphorous and carried metal IMF structure molecular screen is obtained.

According to the disclosure, sodium form IMF structure molecular screen be it is well-known to those skilled in the art, can it is commercially available can be voluntarily Preparation, for example, the preparation step of sodium form IMF structure molecular screen described in step a includes: that will use to have IMF obtained by amine method crystallization After structure molecular screen slurries are filtered and washed, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and with the washing molecule Sodium content % heavy less than 3.0 on the basis of total dry weight of sieve, in the washing molecular sieve；The washing molecular sieve is carried out After dry and air roasting, the sodium form IMF structure molecular screen is obtained.It is described to there is amine method crystallization to refer to using template progress water Thermal crystallisation prepares molecular sieve, by taking the preparation of IMF molecular sieve as an example, specific document can with reference to Chinese patent CN102452667A, CN103708491A, CN102452666A and CN103723740A.The air roasting is used to remove the mould in washing molecular sieve Plate agent, the temperature of the air roasting can be 400-700 DEG C, and the time can be 0.5-10 hours.

According to the disclosure, part framework silicon atom and part framework silicon of the desiliconization processing for removing molecular sieve are removed, It is unobstructed to reach molecular sieve pore passage, generates more second hole effects, aqueous slkali described in step a can be for selected from sodium hydroxide water At least one of solution, potassium hydroxide aqueous solution and ammonium hydroxide, preferably sodium hydrate aqueous solution；At desiliconization described in step a The condition of reason may include: with the water in the alkali and aqueous slkali in the sodium form IMF structure molecular screen of dry basis, aqueous slkali Weight ratio is 1:(0.1-2): (5-20), preferably 1:(0.2-1): the temperature of (5-20), the desiliconization processing are room temperature to 100 DEG C, the time is 0.2-4 hours.

According to the disclosure, ammonium exchange be it is well-known to those skilled in the art, for reducing the sodium content in molecular sieve.Example Such as, the condition of the ammonium exchange may include: according to molecular sieve: ammonium salt: water=1:(0.1-1): the weight ratio of (5-15) will divide Son sieve filters after room temperature exchanges 0.5-3 hours to ammonium at 100 DEG C, and ammonium salt used can be common inorganic ammonium salt, for example, Selected from least one of ammonium chloride, ammonium sulfate and ammonium nitrate, the number of ammonium exchange can be repeated 1-3 times, until in molecular sieve Sodium oxide content is lower than 0.2 heavy %.

According to the disclosure, although desiliconization processing can make molecular sieve generate second hole, in desiliconization treatment process, point Amorphous chips are inevitably resulted from son sieve, block molecular sieve pore passage, cover activated centre, and molecular sieve table can be made The relatively rich aluminium in face, is unfavorable for the raising of molecular sieve reaction selectivity, it is therefore desirable to carry out subsequent dealumination treatment, dealumination treatment to it It is well-known to those skilled in the art, but did not reported and inorganic acid, organic acid and fluosilicic acid are used for dealumination treatment together.Institute It states dealumination treatment can be primary or to be performed in multiple times, organic acid can be exchanged first to molecular sieve with the ammonium and mixed, then by fluorine Silicic acid and inorganic acid exchange molecular sieve mixing with the ammonium, it can exchange in molecular sieve for ammonium first is added in organic acid, then By fluosilicic acid and inorganic acid, cocurrent is added at a slow speed, or fluosilicic acid is first added and adds inorganic acid, preferably fluosilicic acid and inorganic acid Cocurrent is added at a slow speed.For example, organic acid described in step c can be for selected from ethylenediamine tetra-acetic acid, oxalic acid, citric acid and sulfo group water At least one of poplar acid, preferably oxalic acid or citric acid, further preferably oxalic acid；The inorganic acid can be for selected from salt At least one of acid, sulfuric acid and nitric acid, preferably hydrochloric acid or sulfuric acid, further preferably hydrochloric acid；The item of the dealumination treatment Part may include: the weight ratio with the ammonium exchange molecular sieve of dry basis, organic acid, inorganic acid and fluosilicic acid for 1: (0.01-0.3): (0.01-0.3): (0.01-0.3), preferably 1:(0.02-0.2): (0.015-0.2): (0.015-0.2)； The temperature of the dealumination treatment is 25-100 DEG C, and the time is 0.5-6 hours.It is de- by desiliconization processing and Compound-acid dealuminzation agent solution Aluminium processing is combined and is handled IMF structure molecular screen, be distributed the aluminium of molecular sieve, silica alumina ratio, Acidity and pore structure into It has gone modulation, has kept IMF structure molecular screen reaming modified, still there is preferable selective activization, to effectively improve IMF Propylene, ethylene and the BTX yield of structure molecular screen.

According to the disclosure, P Modification processing be it is well-known to those skilled in the art, for example, P Modification described in step d Processing may include: will selected from least one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound to point Son sieve carries out dipping and/or ion exchange.

According to disclosed method, the load of carried metal processing be it is well-known to those skilled in the art, referring to will be preceding The carried metal stated is loaded on the molecular sieve by mode of loading, for example, can will containing selected from iron, cobalt, nickel, copper, manganese, The carried metal is loaded to described point by dipping method by the compound of at least one of zinc, tin, bismuth and gallium carried metal On son sieve；The mode of loading also may include other common metal carrying methods, and the disclosure is not restricted.

According to the disclosure, calcination process is well-known to those skilled in the art, for example, the condition of the calcination process can To include: the atmosphere of calcination process as air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.

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 The water of molecular sieve elutes molecular sieve.

According to the disclosure, the preparation step of the phosphorus aluminium inorganic binder for containing the first clay may include: (1), by oxygen Change silicon source, the first clay and water mashing and is dispersed into the slurries that solid content is 8-45 weight %；The alumina source is can be sour The aluminium hydroxide and/or aluminium oxide of peptization, with the first clay of dry basis and with Al₂O₃The weight ratio of the alumina source of meter For (be greater than 0-40): (15-40)；(2), stirring is lower adds into the slurries that step (1) obtains according to the weight ratio of P/Al=1-6 Enter concentrated phosphoric acid；Wherein in the P/Al P be the phosphorus in terms of simple substance in phosphoric acid weight, Al be in alumina source in terms of simple substance Aluminium weight；(3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.

According to the disclosure, the alumina source can be for selected from ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gamma oxidation Aluminium, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and quasi- At least one of boehmite, the aluminium component in the phosphorus aluminium inorganic binder for containing the first clay are originated from the aluminium oxide Source.First clay can be one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite Or a variety of, preferably rectorite.Its concentration of the concentrated phosphoric acid can be 60-98 weight %, more preferably 75-90 weight %. The charging rate of phosphoric acid is preferably 0.01-0.10Kg phosphoric acid/minute/Kg alumina source, more preferably 0.03-0.07Kg phosphoric acid/ Minute/Kg alumina source.

According to the disclosure, the phosphorus aluminium inorganic binder for containing the first clay was not only being prepared due to the introducing of clay Mass transfer, the heat transfer that storeroom is improved in journey avoid material and unevenly glue caused by local moment vigorous reaction heat release overtemperature Agent solidification is tied, the adhesive property of obtained binder is suitable with the phosphorus al binder for not introducing clay mitigation preparation；And the party Method introduces clay and improves the heavy oil conversion performance of carbon monoxide-olefin polymeric especially with the rectorite of layer structure, make to obtain Auxiliary agent have it is more preferably selective.

The preparation method for the assistant for calalytic cracking that the disclosure provides, by phosphorous and carried metal IMF structure molecular screen, phosphorus aluminium Inorganic binder and the mixing of other inorganic binders, the sequence of mashing, charging do not have a particular/special requirement, for example, can by phosphorus aluminium without Machine binder, other inorganic binders, molecular sieve, the mixing of the second clay (then can be omitted phase when being free of the second clay The addition step of pass) mashing, it is preferred that add again after being first mixed with beating the second clay, molecular sieve and other inorganic binders Enter the phosphorus aluminium inorganic binder, this is conducive to the activity and selectivity for improving auxiliary agent.

The assistant for calalytic cracking preparation method that the disclosure provides further includes being spray-dried the obtained slurries that are beaten Step.The method of spray drying is known to those skilled in the art, the disclosure does not have particular/special requirement.

In the preparation method of assistant for calalytic cracking provided by the disclosure, it can be introduced by way of introducing metallic compound The metallic addition, metallic addition can be in any steps before the spray drying forming of auxiliary agent preparation process toward slurry Metallic compound is added in liquid and is introduced；Dipping or chemisorbed metallic can also be passed through after auxiliary agent spray drying forming Close object after roast and introduce, including by auxiliary agent with metal-containing compound aqueous solution carry out dipping or chemisorption handle, then into Row is separated by solid-liquid separation (if necessary), dry and roasting, wherein dry temperature can be room temperature to 400 DEG C, preferably 100- 300 DEG C, the temperature of roasting can be 400-700 DEG C, and preferably 450-650 DEG C, calcining time can be 0.5-100 hours, excellent It is selected as 0.5-10 hours.The metallic compound is selected from one of their inorganic compound and organic compound or more Kind, it can be soluble easily in water, be also possible to be insoluble in water or compound not soluble in water.The example of metallic compound includes gold Oxide, hydroxide, chloride, nitrate, sulfate, phosphate, organic compound of metal of category etc..Preferred metal Compound is selected from one of their chloride, nitrate, sulfate and phosphate or a variety of.

In assistant for calalytic cracking provided by the disclosure, the metallic addition can reside in auxiliary agent it is any there may be Position, such as can reside in inside the duct of zeolite, the surface of zeolite, can reside in host material, can also be simultaneously It is present in inside the duct of zeolite, in the surface of zeolite and the host material, is preferably in host material.The gold Belonging to additive can exist in the form of their oxide, orthophosphates, phosphite, subphosphate and acid phosphate etc..

Assistant for calalytic cracking preparation method provided by the disclosure, when containing phosphorus additive in auxiliary agent, the phosphorus adds Add agent that can introduce using the combination of one of following method or several method, but is not limited to these methods and introduces auxiliary agent In:

1, phosphorus compound is added in slurries in going to for auxiliary agent spray drying forming；

2, through dipping or chemisorption phosphorus compound after auxiliary agent spray drying forming, through being separated by solid-liquid separation (if necessary If), dry and roasting process introduce, the temperature of the drying can be room temperature to 400 DEG C, preferably 100-300 DEG C, roasting Temperature can be 400-700 DEG C, and preferably 450-650 DEG C, calcining time can be 0.5-100 hours, and preferably 0.5-10 is small When.The phosphorus compound can be selected from one of various inorganic compounds and organic compound of phosphorus or a variety of.The phosphatization Closing object can be soluble easily in water, be also possible to be insoluble in water or phosphorus compound not soluble in water.The embodiment packet of phosphorus compound Include oxide, phosphoric acid, orthophosphates, phosphite, hypophosphites, the phosphorous organic compound etc. of phosphorus.Preferred phosphatization is closed Object is selected from one of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and aluminum phosphate or a variety of.

Thus, the phosphorus additive can reside in any position that may be present of auxiliary agent, as can reside in zeolite Inside duct, the surface of zeolite, can reside in the host material, can also exist simultaneously inside the duct of zeolite, In the surface of zeolite and the host material.The phosphorus additive is with phosphorus compound (oxide of such as phosphorus, orthophosphates, phosphorous Hydrochlorate, subphosphate, acid phosphate) form exist.

The assistant for calalytic cracking that the disclosure provides is suitable for various hydrocarbon oil catalytic crackings.It, can when for catalytic cracking process Individually toward adding in catalyst cracker, used after can also being mixed with catalytic cracking catalyst.Under normal circumstances, the disclosure mentions The auxiliary agent of confession accounts for FCC catalyst and the agent mixture total amount of disclosure offer is no more than 30 weight %, preferably 1-25 weight Measure %, more preferably 3-15 weight %, the hydrocarbon ils be selected from various petroleum distillates, as crude oil, reduced crude, decompression residuum, often Press wax oil, decompressed wax oil, straight-run gas oil, propane it is light/one of de-oiling, wax tailings and coal liquefaction products or a variety of again.Institute Stating hydrocarbon ils can be containing beavy metal impurities and sulphur, nitrogen impurity such as nickel, vanadium, as the content of sulphur may be up to 3.0 weight %, the content of nitrogen The content of up to 2.0 weight %, the metal impurities such as vanadium, nickel may be up to 3000ppm.

The assistant for calalytic cracking that the disclosure provides is in catalytic cracking process, hydrocarbon oil catalytic cracking condition to be conventional urges Change cracking conditions.In general, it is 400-600 DEG C which, which includes reaction temperature, preferably 450-550 DEG C, weight (hourly) space velocity (WHSV) is 8-120 hours^-1, preferably 8-80 hours^-1, oil ratio (weight ratio) is 1-20, preferably 3-15.This public affairs The assistant for calalytic cracking for opening offer can be used for existing various catalyst crackers, such as anti-in fixed bed reactors, fluidized bed It answers and is carried out in device, riser reactor, multi-reaction-area reactor etc..

The disclosure is further illustrated below by embodiment, but therefore the disclosure is not any way limited, this Instrument and reagent used by open embodiment are unless otherwise instructed instrument and examination commonly used by those skilled in the art Agent.

The crystallinity of the disclosure is measured using the standard method of ASTM D5758-2001 (2011) e1.

The phosphorus content of the disclosure is measured using GB/T 30905-2014 standard method, and the content of carried metal uses GB/T 30905-2014 standard method is measured.

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

Total specific surface (S of the disclosure_BET), mesoporous pore volume, total pore volume, 2-20 nanometers mesoporous pore volume use The AS-3 of Quantachrome instrument company production, the measurement of AS-6 static state n2 absorption apparatus.Instrument parameter: sample is placed at sample Reason system is evacuated to 1.33 × 10 at 300 DEG C^-2Pa, heat-insulation pressure keeping 4h purify sample.At -196 DEG C of liquid nitrogen temperature, survey Examination purification sample is not pressing P/P on year-on-year basis₀Under the conditions of to the adsorbance and desorption rate of nitrogen, obtain N₂Adsorption-desorption isothermal curve. Then total specific surface area, micropore specific area and mesopore surface area are calculated using two parameter BET formula, taken than pressing P/P₀= 0.98 adsorbance below is the total pore volume of sample, the pore-size distribution of mesoporous part is calculated using BJH formula, and using integral Method calculates mesoporous pore volume (2-100 nanometers) and 2-20 nanometers of mesoporous pore volume.

The strong acid acid amount and total acid content of the disclosure use II 2920 temperature programmed desorption of Merck & Co., Inc, U.S. Autochem Instrument is measured.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) is warming up to 600 DEG C with the rate of 20 DEG C/min, and purging 60min drives away the impurity of catalyst surface absorption.Then 100 DEG C are cooled to, constant temperature 30min switches to NH₃- He gaseous mixture (10.02%NH₃+ 89.98%He) absorption 30min, it is further continued for It is steady to baseline that 90min is swept with He air-blowing, the ammonia of physical absorption is desorbed.600 DEG C are warming up to 10 DEG C/min heating rate It is desorbed, keeps 30min, desorption terminates.Using TCD detector detection gas change of component, instrument automatic integration is obtained always Acid amount 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 B acid acid amount of the disclosure and L acid acid amount are infrared using the FTS3000 type Fourier of U.S. BIO-RAD company production Spectrometer is measured.Test condition: tabletted be placed in the pond in situ of infrared spectrometer of sample is sealed, at 350 DEG C Under be evacuated to 10^-3Pa keeps 1h, the gas molecule of sample surfaces is desorbed clean, is cooled to room temperature.It is imported into pond in situ Pressure is that the pyridine steam of 2.67Pa is warming up to 200 DEG C, is evacuated to 10 again after balancing 30min^-3Pa keeps 30min, cold But to room temperature, in 1400-1700cm^-1Scanning, records the infrared spectrum spectrogram of 200 DEG C of pyridine adsorptions in wave-number range.Again will Sample in cell for infrared absorption moves to heat-treatment zone, is warming up to 350 DEG C, is evacuated to 10^-3Pa keeps 30min, is cooled to room temperature, Record the infrared spectrum of 350 DEG C of pyridine adsorptions.Instrument automatic integration obtains B acid acid amount and L acid acid amount.

The sodium content of the disclosure is measured using GB/T 30905-2014 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.

For the auxiliary agent of the disclosure when being used for catalytic cracking reaction performance evaluation, reaction product is by N₂- 10 DEG C of liquid is brought into receive Gas-liquid separation is carried out in bottle, gaseous product, which is collected, to be completed to be made of Agilent 6890GC (TCD detector) on-line analysis；Liquid Weighed off line after collection of products, carries out simulation distillation respectively and gasoline detailed hydrocarbon analysis (is carried out using RIPP81-90 test method Test), the fraction cut point of gasoline and diesel oil is respectively 221 DEG C and 343 DEG C；The regeneration of green coke catalyst on-line decoking, and according to Flue gas flow and composition calculate coke quality；All product quality adductions calculate material balance.

For details, reference can be made to " petrochemical analysis method ", Yang Cui is surely equal to be compiled for RIPP standard method described in the disclosure, and 1990 Year version.

Part material property used in embodiment is as follows:

Boehmite is that Shandong Aluminium Industrial Corp produces industrial products, 60 weight % of solid content；Aluminum sol is that middle petrochemical industry is urged The industrial products of agent asphalt in Shenli Refinery production, Al₂O₃Content is 21.5 weight %；Silica solution is middle Effect of Catalysis In Petrochemistry agent Shandong point The industrial products of company's production, SiO₂Content is 28.9 weight %, Na₂O content 8.9%；Kaolin is raw for Kaolin of Suzhou company The dedicated kaolin of the catalytic cracking catalyst of production, solid content are 78 weight %.Concentration of hydrochloric acid is 36 weight %, and rectorite is Hubei Distinguished personages' rectorite development corporation, Ltd., Zhongxiang City product, quartz sand content < 3.5 weight %, Al₂O₃Content is 39.0 weight %, Fe₂O₃Content is 2.0 weight %, Na₂O content is 0.03 weight %, and solid content is 77 weight %；SB aluminium hydrate powder: Germany The production of Condex company, Al₂O₃Content is 75 weight %；Gamma oxidation aluminium powder: German Condex company production, Al₂O₃Content is 95 weight %.Hydrochloric acid: chemistry is pure, and concentration is 36-38 weight %, Beijing Chemical Plant's production.

Embodiment 1-2 provides the phosphorous and carried metal IMF structure molecular screen of the disclosure, and comparative example 1-8 is provided to score Son sieve.

Embodiment 1

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 6 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.4 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 5g are added in stirring, then by 35g hydrochloric acid (mass fraction 10%) and 28g fluosilicic acid (mass fraction 3%) cocurrent are added, and time 30min is added；65 DEG C of constant temperature are warming up to stir 1h is mixed, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3g H₃PO₄(85 weight % of concentration) and 3.3gZn (NO₃)₂·6H₂O is uniformly mixed with dipping, drying, 550 DEG C of calcination process 2h, score Son sieve A, physico-chemical property are listed in table 1.

Comparative example 1

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.4 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, and oxalic acid 20g is added in stirring；It is warming up to 65 DEG C of perseverances Temperature stirring 1h, filtering are washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.1gH₃PO₄(85 weight % of concentration) and 3.3gZn (NO₃)₂·6H₂O, uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small When.Molecular sieve DA1 is obtained, physico-chemical property is listed in table 1.

Comparative example 2

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.2 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then obtained molecular sieve filter cake is added in HCL aqueous solution and is washed, it is specific to grasp As the molecular sieve pulp for taking above-mentioned molecular sieve filter cake 50g (butt) plus water to be configured to the weight of solid content 10 %, it is added in stirring 180g hydrochloric acid (mass fraction 10%)；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；1500g is added in filter cake Water mashing, is added 80g NH₄After Cl is warming up to 65 DEG C of exchange washing 40min, filtering, elution to filtrate neutrality；By filter cake plus water It is beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight % of concentration) and 3.3gZn (NO₃)₂· 6H₂O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA2 is obtained, physico-chemical property is listed in table 1.

Comparative example 3

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.2 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, and 135g fluosilicic acid (mass fraction is added in stirring 3%) time 30min, is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；Filter cake plus water are beaten solid Content is the molecular sieve pulp of 40 weight %, and 6.3gH is added₃PO₄(85 weight % of concentration) and 3.3gZn (NO₃)₂·6H₂O, it is uniformly mixed Close dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA3 is obtained, physico-chemical property is listed in table 1.

Comparative example 4

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 1.9 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 11g are added in stirring, then by 110g salt Sour (mass fraction 10%) is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to filtrate neutrality；It will Filter cake adds water to be beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight % of concentration) and 3.3gZn (NO₃)₂·6H₂O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA4 is obtained, physico-chemical property is listed in table 1.

Comparative example 5

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.0 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, oxalic acid 4g are added in stirring, then by 72g fluorine silicon Sour (mass fraction 3%) is slowly added to, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed in filtrate Property；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight % of concentration) 3.3gZn(NO₃)₂·6H₂O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve DA5, physico-chemical property column In table 1.

Comparative example 6

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.0 weight % of 1000g, is warming up to 65 DEG C, after reacting 30min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, under stirring by 42g hydrochloric acid (mass fraction 10%) and 78g fluosilicic acid (mass fraction 3%) cocurrent is added, and time 30min is added；65 DEG C of constant temperature stirring 1h are warming up to, filtering is washed to Filtrate is neutral；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight of concentration Measure %) and 3.3gZn (NO₃)₂·6H₂O, uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Obtain molecular sieve DA6, object Change property and is listed in table 1.

Comparative example 7

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；By above-mentioned baking Molecular sieve roasts 8 hours in air after dry, and 550 DEG C of maturing temperature, to remove template therein.Take above-mentioned molecular sieve 100g It is added in the NaOH solution of 1.2 weight % of 2000g, is warming up to 65 DEG C, after reacting 30min, be rapidly cooled to room temperature, filter, wash It washs to filtrate neutrality.It takes above-mentioned molecular sieve filter cake 50g (butt) that the mashing of 500g water is added, 40g NH is added₄Cl is warming up to 75 DEG C, after exchange processing 1h, filtering, repeated exchanged is washed twice to molecular sieve sodium oxide content lower than 0.1%, and filter cake plus water are beaten Starch to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight % of concentration) and 3.3gZn (NO₃)₂·6H₂O, Uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours.Molecular sieve DA7 is obtained, physico-chemical property is listed in table 1.

Embodiment 2

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.3 weight % of 1500g, is warming up to 60 DEG C, after reacting 45min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 4g are added in stirring, then 10g sulfuric acid (mass fraction 10%) and 45g fluosilicic acid (mass fraction 3%) cocurrent are added, and time 30min is added；45 DEG C of constant temperature are warming up to stir 1h is mixed, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight % of concentration) and 4.1gFe (NO₃)₃·9H₂O, uniformly hybrid infusion, drying, 550 DEG C of calcination process 2 are small When.Molecular sieve B is obtained, physico-chemical property is listed in table 1.

Comparative example 8

The good IM-5 molecular sieve of crystallization (production of Chang Ling catalyst plant) is filtered out into mother liquor, washing filtering drying；It will be above-mentioned Molecular sieve roasts 8 hours in air after drying, and 550 DEG C of maturing temperature, to remove template therein；Take above-mentioned molecular sieve 100g (butt) is added in the NaOH solution of 2.3 weight % of 1500g, is warming up to 60 DEG C, after reacting 45min, is quickly cooled to room Wen Hou, filtering, washing to filtrate neutrality.Then, the mashing of 800g water is added in filter cake, 40g NH is added₄Cl is warming up to 75 DEG C, After exchange processing 1h, until Na₂O content is lower than 0.2 weight %, filters, and washing obtains molecular sieve filter cake；Take above-mentioned molecule sieving Cake 50g (butt) plus water are configured to the molecular sieve pulp of the weight of solid content 10 %, citric acid 4g are added in stirring, then 10g sulfuric acid (mass fraction 10%) and 45g fluosilicic acid (mass fraction 3%) cocurrent are added, and time 30min is added；45 DEG C of constant temperature are warming up to stir 1h is mixed, filtering is washed to filtrate neutrality；Filter cake plus water are beaten to obtain molecular sieve pulp of the solid content for 40 weight %, addition 6.3gH₃PO₄(85 weight % of concentration), uniformly be mixed with dipping, drying, 550 DEG C calcination process 2 hours, obtain molecular sieve DB1, materialization Property is listed in table 1.

IM-5 molecular sieve surface richness aluminium will be made using conventional alkali process it can be seen from data in table 1, and used single Organic acid oxalic acid dealuminzation (DA1) uses single inorganic acid HCl dealumination (DA2) and uses organic acid oxalic acid and inorganic acid salt Sour two kinds of acid compound (DA4) all can not effectively remove the Al in molecular sieve, molecular sieve still surface richness aluminium and only use Preferable dealuminzation effect could be obtained after fluosilicic acid, improve the distribution of molecular sieve aluminium.When fluosilicic acid dealuminzation is used alone (DA3), The aluminium distribution of molecular sieve can be improved, but mesoporous is still relatively fewer, strong acid proportion in total acid is lower, B acid/L acid ratio Example is lower.Fluosilicic acid composite organic acid oxalic acid dealuminzation (DA5) is equally unable to get higher mesopore proportion and preferable acidity point Cloth.Fluosilicic acid composite inorganic acid HCl dealumination (DA6), although mesopore volume increased, strong acid institute's accounting in total acid The molecular sieve that example and B acid/L acid ratio are all not so good as disclosure offer is high.The disclosure is using first to molecular sieve progress desiliconization processing Afterwards, compound acid system is reused, dealumination treatment is carried out under three kinds of sour synergistic effects, can guarantee crystal structure of molecular sieve With the distribution of improvement aluminium and acid distribution under the premise of mesopore orbit structural intergrity.Molecular sieve impregnating metal increases dehydrogenation function Energy.

Embodiment 3-6 provides phosphorus aluminium inorganic binder used in the disclosure.

Embodiment 3

The present embodiment prepares phosphorus aluminium inorganic binder described in the disclosure.

1.91 kilograms of boehmites (are contained into Al₂O₃1.19 kilograms), 0.56 kilogram of kaolin (0.50 kilogram of butt) with 3.27 kilograms of decationized Y sieve water are beaten 30 minutes, and stirring is lower, and 5.37 kilograms of concentrated phosphoric acids (mass concentration 85%) are added into slurries, It is 0.04Kg phosphoric acid/minute/Kg alumina source that speed, which is added, in phosphoric acid, is warming up to 70 DEG C, is then reacted 45 minutes at this temperature, Obtain phosphorus aluminium inorganic binder.Material proportion is shown in Table 2, obtains binder Binder1.

Embodiment 4-6

Phosphorus aluminium inorganic binder is prepared as described in Example 3, and material proportion is shown in Table 2, obtains binder Binder2-4.

Embodiment 7-11 provides the assistant for calalytic cracking of the disclosure, and comparative example 9-16 provides comparison assistant for calalytic cracking.

Embodiment 7

Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring Lower addition FeCl₃·6H₂Aqueous solution (the FeCl of O₃30 weight % of content), the slurries of 30 weight % of solid content are obtained, hydrochloric acid is added The pH value 3.0 for adjusting slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 3, stirring is then added After 30 minutes, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made₁, match Than being shown in Table 3.

Embodiment 8

Molecular sieve B, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring Lower addition FeCl₃·6H₂Aqueous solution (the FeCl of O₃30 weight % of content), the slurries of 30 weight % of solid content are obtained, hydrochloric acid is added The pH value 3.0 for adjusting slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 3, stirring is then added After 30 minutes, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made₂, match Than being shown in Table 3.

Embodiment 9

Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, obtains The slurries of 30 weight % of solid content, are added the pH value 3.0 that hydrochloric acid adjusts slurries, then proceed to mashing 45 minutes, are then added real Apply example 4 preparation phosphorus aluminium inorganic binder, stirring 30 minutes after, by obtained slurries be spray-dried, obtain microballoon, by microballoon in It is roasted 1 hour at 500 DEG C.Thus obtained microsphere product is taken, ZnCl is added₂Aqueous solution (30 weight % of concentration), is warming up to 60 under stirring DEG C, it reacts at this temperature after twenty minutes, then slurries vacuum filter, drying roasts 2 hours at 500 DEG C, ZJ is made₃, Its proportion is shown in Table 3.

Embodiment 10

Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and silica solution is beaten 120 minutes, stirring Lower addition Co (NO₃)₂·6H₂The aqueous solution (30 weight % of concentration) of O obtains the slurries of 30 weight % of solid content, and hydrochloric acid tune is added The pH value 3.0 for saving slurries then proceedes to mashing 45 minutes, and phosphorus aluminium inorganic binder prepared by embodiment 5, stirring 30 is then added After minute, obtained slurries are spray-dried, microballoon is obtained, microballoon is roasted 1 hour at 500 DEG C, ZJ is made₄, proportion It is shown in Table 3.

Embodiment 11

Molecular sieve-4 A, kaolin and boehmite are taken, decationized Y sieve water is added and Aluminum sol is beaten 120 minutes, stirring Lower addition Ga (NO₃)₃Aqueous solution (30 weight % of concentration), obtain the slurries of 30 weight % of solid content, hydrochloric acid be added and adjusts slurries PH value 2.5, then proceed to mashing 45 minutes, then be added embodiment 6 prepare phosphorus aluminium inorganic binder, stir 30 minutes Afterwards, obtained slurries are spray-dried, obtain microballoon.The phosphoric acid hydrogen two that concentration is 7.5 weight % is added in thus obtained microsphere product In aqueous ammonium, 60 DEG C are warming up under stirring, is reacted at this temperature after twenty minutes, by slurries vacuum filter, drying, then in It is roasted 2 hours at 500 DEG C, auxiliary agent ZJ is made₅, auxiliary agent proportion be shown in Table 3.

Comparative example 9-16

Prepare assistant for calalytic cracking by method described in embodiment 7, be a difference in that with molecular sieve DA1, DA2, DA3, DA4, DA5, DA6, DA7, DB1 replace A respectively, and auxiliary agent DZJ is made₁-DZJ₈, match and be shown in Table 3.

Skip test example, embodiment 12-16 are using small fixed flowing bed-tion reacting device to 100% poising agent and balance Agent mixes auxiliary agent ZJ prepared by the embodiment of the present disclosure₁-ZJ₅Reactivity worth evaluation is carried out, is split with the catalysis for illustrating that the disclosure provides Change the catalytic cracking reaction effect of auxiliary agent.

Skip test example, embodiment 12-16

Respectively by auxiliary agent ZJ₁-ZJ₅17 hours aging processs are carried out under the conditions of 800 DEG C, 100% steam atmosphere.It takes ZJ through aging process₁-ZJ₆(the industrial trade mark is the FCC equilibrium catalyst of DVR-3, micro-activity with industrial FCC equilibrium catalyst 63) to mix respectively.100% poising agent and catalyst mixture are fitted into small fixed flowing bed reactor, to shown in table 4 Feedstock oil carries out catalytic cracking, reaction condition are as follows: and 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 8h^-1, agent oil weight ratio 6.Table 5 gives The weight of each catalyst mixture forms and reaction result.

Comparative example 17-24 is using small fixed flowing bed-tion reacting device to prepared by poising agent incorporation disclosure comparative example Auxiliary agent DZJ₁-DZJ₈The case where having carried out performance evaluation, comparison auxiliary agent used with explanation.

Comparative example 17-24

Catalytic cracking is carried out to same feedstock oil by the method in embodiment 12, the difference is that used catalyst is respectively Auxiliary agent DZJ after aging method aging identical in embodiment 12₁-DZJ₈With the mixture of industrial FCC equilibrium catalyst.Table 6 Give the weight composition and reaction result of each catalyst mixture.

It can be seen from table 5 and table 6 compared with comparing auxiliary agent, the catalyst aid that the disclosure provides can effectively increase and urge Change cracking propylene and liquefied gas yield, while significant the density of propylene improved in catalytic cracking liquefied gas.

Table 1

Molecular sieve	A	DA1	DA2	DA3	DA4	DA5	DA6	DA7	B	DB1
											Crystallinity/%	87	80	78	83	83	83	85	83	89	90
P₂O₅Content/%	7.5	7.2	7.5	7.5	7.5	7.5	7.5	7.5	7.5	7.5
											Metal oxide content/%	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0
S_BET/(m²/g)	508	460	447	470	466	472	487	410	517	521
											(V_Mesoporous/V_{Total hole})/%	60.0	53.2	54.1	56.8	54.2	56.3	57.0	52.1	61.7	62.3
(V_2nm-20nm/V_Mesoporous)/%	90	80	80	86	77	82	82	63	92	92
											(strong acid acid amount/total acid content)/%	62	46	45	55	43	56	53	38	64	65
The sour amount of B acid/L acid acid amount	12.8	4.6	4.8	7.7	4.8	9.8	8.8	2.1	13.7	14.2
											D (Al distribution)	0.75	1.1	1.1	0.95	1.1	0.87	0.91	1.1	0.80	0.80

Table 2

Table 3

Table 4

Density, g/cm³(20℃)	0.9171
		Viscosity (100C), mm²/s	10.61
Condensation point, DEG C	20
		Carbon residue, weight %	1.91
Constituent content, weight %
		C	85.96
H	12.37
		S	1.0
N	0.35
		Tenor, μ g/g
Ca	8.3
		Fe	12.3
Na	0.9
		Ni	4.7
V	0.4
		Boiling range, DEG C
Initial boiling point	267
		10%	371
50%	449
		70%	486
86.9%	549

Table 5

Table 6

Claims

1. a kind of assistant for calalytic cracking of propylene enhancing, on the basis of the dry weight of the auxiliary agent, which includes with butt The phosphorous and carried metal IMF structure molecular screen of poidometer 10-75 weight %, with the phosphorus aluminium of dry basis 3-40 weight % without Machine binder, other inorganic binders of the weight of the 1-30 in terms of oxide % are viscous with the second of dry basis 0-60 weight % Soil, and the metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of the weight of the 0.5-15 in terms of oxide %； Wherein,

The phosphorus aluminium inorganic binder is phosphorus aluminium glue and/or the phosphorus aluminium inorganic binder containing the first clay, contains first with described On the basis of the phosphorus aluminium inorganic binder dry weight of clay, the phosphorus aluminium inorganic binder for containing the first clay includes with Al₂O₃Meter 15-40 weight % aluminium component, with P₂O₅It counts the phosphorus component of 45-80 weight % and is greater than 0 with dry basis and is no more than 40 weights The first clay of % is measured, and its P/Al weight ratio is 1.0-6.0, pH value 1-3.5, solid content is 15-60 weight %；

The Al distribution parameter D of the molecular sieve meets: 0.6≤D≤0.85；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 total mesopore volume of the molecular sieve accounts for total pore volume is 50-80%, and aperture is in 2 nanometers -20 nanometers The ratio of the total mesopore volume of pore volume Zhan is greater than 85%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 50-80%, The ratio between B acid acid amount and L acid acid amount are 7-30；With P₂O₅Count and on the basis of the dry weight of molecular sieve, the phosphorus of the molecular sieve contains Amount is 0.1-15 weight %；It is counted by the oxide of the carried metal and on the basis of the dry weight of the molecular sieve, it is described Carried metal content is 0.1-5 weight % in molecular sieve；Total mesopore volume finger-hole diameter is greater than 2 nanometers less than 100 nanometers Pore volume.

2. auxiliary agent according to claim 1, wherein the Al distribution parameter D of the molecular sieve meets: 0.65≤D≤0.82； The ratio that total mesopore volume of the molecular sieve accounts for total pore volume is 57-70%, the mesopore volume that aperture is 2 nanometers -20 nanometers The ratio of the total mesopore volume of Zhan is greater than 90%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 55-70%, B acid acid The ratio between amount and L acid acid amount are 8-25；With P₂O₅Count and on the basis of the dry weight of molecular sieve, the phosphorus content of the molecular sieve is 1-13 weight %；It is counted by the oxide of the carried metal and on the basis of the dry weight of the molecular sieve, the molecular sieve Middle carried metal content is 0.5-3 weight %.

3. auxiliary agent according to claim 1, wherein the carried metal is selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth At least one of with gallium.

4. auxiliary agent according to claim 1, wherein first clay is selected from kaolin, sepiolite, concave convex rod At least one of stone, rectorite, montmorillonite and diatomite；Second clay is selected from kaolin, metakaolin, diatom At least one of soil, sepiolite, attapulgite, montmorillonite and rectorite；Other inorganic binders are selected from intending thin water At least one of aluminium stone, Aluminum sol, silicon-aluminum sol and waterglass.

5. auxiliary agent according to claim 1, wherein the metallic addition introduced in the form of metallic compound described in help Agent, the metallic compound are selected from oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound At least one of object.

6. auxiliary agent described in any one of -5 according to claim 1, wherein on the basis of the dry weight of the auxiliary agent, institute Auxiliary agent is stated also to contain with P₂O₅Meter is no more than the phosphorus additive of 5 weight %.

7. auxiliary agent according to claim 6, wherein the auxiliary agent includes phosphorus aluminium inorganic binder, the 20- of 8-25 weight % The phosphorous and carried metal IMF structure molecular screen of 60 weight %, the second clay of 10-45 weight %, 5-25 weight % it is other The phosphorus additive of inorganic binder, the metallic addition of 1.0-10 weight % and 0-3 weight %.

8. a kind of preparation method of the assistant for calalytic cracking of propylene enhancing, this method comprises:

Phosphorous and carried metal IMF structure molecular screen, phosphorus aluminium inorganic binder and other inorganic binders are mixed, adds or is not added Enter the second clay, is beaten, spray drying；Wherein, metallic addition is introduced, phosphorus additive is introduced or do not introduce；

On the basis of the total dry weight for preparing raw material of auxiliary agent, the raw material for preparing of the auxiliary agent includes with dry basis 10- The phosphorous and carried metal IMF structure molecular screen of 75 weight %, with the phosphorus aluminium inorganic binder of dry basis 3-40 weight %, Other inorganic binders of the weight of the 1-30 in terms of oxide %, with the second clay of dry basis 0-60 weight %, with oxidation The metallic addition selected from least one of VIII race's metal and manganese, zinc, gallium of object meter 0.5-15 weight %, and including or not Including with P₂O₅Meter is no more than the phosphorus additive of 5 weight %；Wherein,

9. preparation method according to claim 8, wherein described phosphorous and carried metal IMF structure molecular screen preparation Step includes:

A, sodium form IMF structure molecular screen is subjected in aqueous slkali desiliconization processing, obtains desiliconization molecular sieve；

B, gained desiliconization molecular sieve in step a is subjected to ammonium exchange processing, obtains ammonium exchange molecular sieve；Wherein, in terms of sodium oxide molybdena And on the basis of total dry weight of ammonium exchange molecular sieve, the sodium content of the ammonium exchange molecular sieve is less than 0.2 weight %；

C, gained ammonium exchange molecular sieve in step b is molten in the Compound-acid dealumination agent being made of fluosilicic acid, organic acid and inorganic acid Dealumination treatment is carried out in liquid, and after being filtered and washed, obtains dealuminzation molecular sieve；

D, it after dealuminzation molecular sieve obtained in step c being carried out P Modification processing, carried metal modification and calcination process, obtains To described phosphorous and carried metal IMF structure molecular screen.

10. preparation method according to claim 9, wherein the preparation of sodium form IMF structure molecular screen described in step a walks Suddenly include:

After will be using there are IMF structure molecular screen slurries obtained by amine method crystallization to be filtered and washed, washing molecular sieve be obtained；Its In, by sodium oxide molybdena count and by it is described washing molecular sieve total dry weight on the basis of, it is described washing molecular sieve in sodium content it is small In 3.0 weight %；

The washing molecular sieve is dried and after air roasting, obtains the sodium form IMF structure molecular screen.

11. preparation method according to claim 9, wherein aqueous slkali described in step a is water-soluble selected from sodium hydroxide At least one of liquid, potassium hydroxide aqueous solution and ammonium hydroxide.

12. preparation method according to claim 9, wherein the condition of the processing of desiliconization described in step a includes: with butt The weight ratio of the water in alkali and aqueous slkali in the sodium form IMF structure molecular screen of poidometer, aqueous slkali is 1:(0.1-2): (5- 20), the temperature of the desiliconization processing is room temperature to 100 DEG C, and the time is 0.2-4 hours.

13. preparation method according to claim 9, wherein the condition of the processing of desiliconization described in step a includes: with butt The weight ratio of the water in alkali and aqueous slkali in the sodium form IMF structure molecular screen of poidometer, aqueous slkali is 1:(0.2-1): (5- 20)。

14. preparation method according to claim 9, wherein organic acid described in step c be selected from ethylenediamine tetra-acetic acid, At least one of oxalic acid, citric acid and sulfosalicylic acid, the inorganic acid are at least one in hydrochloric acid, sulfuric acid and nitric acid Kind.

15. preparation method according to claim 9, wherein the condition of dealumination treatment described in step c includes: with butt The weight ratio that the ammonium of poidometer exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1:(0.01-0.3): (0.01- 0.3): (0.01-0.3)；The temperature of the dealumination treatment is 25-100 DEG C, and the time is 0.5-6 hours.

16. preparation method according to claim 9, wherein the condition of dealumination treatment described in step c includes: with butt The weight ratio that the ammonium of poidometer exchanges molecular sieve, organic acid, inorganic acid and fluosilicic acid is 1:(0.02-0.2): (0.015- 0.2): (0.015-0.2).

17. preparation method according to claim 9, wherein P Modification described in step d processing include: will selected from phosphoric acid, At least one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate phosphorus-containing compound carries out dipping to molecular sieve and/or ion is handed over It changes.

18. preparation method according to claim 9, wherein carried metal modification described in step d includes: that will contain There is the compound selected from least one of iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium carried metal will be described by dipping method Carried metal loads on the molecular sieve.

19. preparation method according to claim 9, wherein the condition of calcination process described in step d includes: at roasting The atmosphere of reason is air atmosphere or steam atmosphere；Maturing temperature is 400-800 DEG C, and calcining time is 0.5-8 hours.

20. preparation method according to claim 8, wherein the preparation of the phosphorus aluminium inorganic binder for containing the first clay Step includes:

(1), alumina source, the first clay and water mashing are dispersed into the slurries that solid content is 8-45 weight %；The oxidation Silicon source be can by the aluminium hydroxide and/or aluminium oxide of sour peptization, relative to be greater than 0 and be no more than 40 parts by weight with dry weight First clay of meter, with Al₂O₃The dosage of the alumina source of meter is 15-40 parts by weight；

(2), stirring is lower is added concentrated phosphoric acid according to the weight ratio of P/Al=1-6 into the slurries that step (1) obtains；

(3), the slurries that step (2) obtains are reacted 15-90 minutes at a temperature of 50-99 DEG C.