CN106732745A - A kind of preparation method of catalytic cracking catalyst - Google Patents

Abstract

A kind of preparation method of catalytic cracking catalyst, it is characterized in that, NaY molecular sieve original powder is contacted and carries out gaseous ion exchange reaction by the method with halogen-containing gas, one step completes the drop sodium and super stabilizing of NaY molecular sieve original powder, low-Na and high-Si aluminum ratio molecular sieve is obtained, the method processes through high concentrated acid after also variety classes clay raw ore is compounded and acid compound clay living is obtained, again by low-Na and high-Si aluminum ratio molecular sieve, acid compound clay and binding agent living, rare earth, mist projection granulating after the mixing mashing of decationizing water, fired solidification, without washing, dry, obtain catalytic cracking catalyst finished product.The catalytic cracking catalyst can significantly reduce olefin(e) centent in gasoline, improve light oil yield, and catalyst preparation flow is short, without ammonia nitrogen discharge.

Description

A kind of preparation method of catalytic cracking catalyst

Technical field

The present invention relates to oil refining catalyst preparing technical field, more particularly to a kind of side for preparing catalytic cracking catalyst Method, is in particular that the super stable molecular sieve prepared on a kind of utilization gaseous ion exchange process is active component, Compound-acid work Clay is activated carrier, there is provided a kind of to be applied to catalytic cracking without ammonia nitrogen discharge, short route, the low sodium of silicon high and high stability Method for preparing catalyst.

Technical background

It is well known that petroleum refining industry is key pillars of the national economy, its industry chain (supply chain) is long, product broad covered area, It is closely bound up with people's lives.And a most important refining means are exactly catalytic cracking technology in petroleum refining process, China 70% gasoline, 40% diesel oil, 40% propylene all derives from catalytic cracking needed for daily, and catalytic cracking catalyst is to urge Change the core content of cracking.

On the other hand, with the heaviness and in poor quality of world's crude quality, and clear gusoline demand is constantly increased Big and environmental requirement increasingly strictly in the case of, people require that catalytic cracking catalyst will have active, more rich two higher Secondary pore structure, heat endurance higher and hydrothermal stability, lower coke yield and sodium content, are turned with obtaining heavy oil higher Rate, yield of light oil higher and total liquid recovery, preferable coke selectivity and catalyst service life more long, and it is right Ammonia nitrogen waste water, the waste gas produced in catalyst preparation process are also strictly controlled.

Simultaneously under the overall situation of global crude oil price continued downturn, because the big ups and downs of crude oil price bring to refinery Enormous impact, domestic product oil price once goes way down and creates rare " eight even fall ".So while the market demand is met how Oil plant is obtained maximum economic benefit, as a problem in the urgent need to address, and reduce the production of Cracking catalyst Cost can also play the purpose for reducing oil refining cost.

And made a general survey of since catalytic cracking technology studies successfully from French scientist E.J. Hu Deli, catalytic cracking catalyst exists The molecular sieve catalyst two that the indefiniteness alumina silicate catalyst and nineteen sixties that early stage is formd in development occur is big Class.Wherein molecular sieve catalyst can divide the original that natural kaolin base portion crystallizes into Y type molecular sieve by raw material and manufacturing process The semi-synthetic molecular sieve catalyst that position crystallization type catalyst, molecular sieve and matrix are prepared respectively.

With the in-situ crystallization technology that natural kaolin prepares NaY type molecular sieves as raw material be initially the nineteen sixty-eights such as Heden by Disclosed in USP3391994.Engelhard companies of the U.S. further study by raw material of kaolin microsphere and pass through in-situ crystallization Method prepare the technique of catalytic cracking catalyst, main disclosure has been done by USP4493902, it is characterized in that first spraying prepare it is high Ridge soil microballoon, then disposably prepares active component (Y type molecular sieve) and carrier (kaolin).The CNPC Lanzhou of China Petro-chemical corporation has also successfully industrialized the original position with independent intellectual property right by independent research in the 1980s Crystallization type catalytic cracking catalyst (also referred to as full clay catalyst), as only this core technology of grasp in the country, realizes work The company of industry.

CN1232862A discloses a kind of all-white clay catalyst for fluid catalytic cracking and preparation method thereof, be characterized in Kaolin is raw material, and through a part of high-temperature roasting of the spray particles after pulp spray shaping, another part is roasted at a lower temperature Burn, two kinds of roasting microballoons mix by a certain percentage, crystallization are carried out in the presence of sodium metasilicate, directed agents etc., the crystallization for obtaining " four hand over two to roast " technique that microballoon is exchanged by ammonium exchange-rare earth exchanged-roasting-rare earth exchanged-roasting-ammonium again obtains catalyst Finished product.

CN1334318A discloses a kind of preparation method of full-clay high octane number catalytic cracking catalyst, is characterized in By crystallization product through " four hand over two to roast " and the super steady modification of hydro-thermal, catalyst prod is obtained.

The method that CN1429882A is disclosed is by kaolin, solid crystal seeds, auxiliary agent, organic dispersing agent or/and binding agent etc. Through mist projection granulating, and in-situ crystallization product obtains catalyst prod through " three hand over one to roast " technique.

It is raw material fabricated in situ catalytic cracking that CN102247880A discloses one kind and uses catalytic cracking spent catalyst fine powder The method of catalyst.

CN102764670A discloses a kind of method that many crystalline phase kaolin microspheres prepare in-situ crystallization type Cracking catalyst, Its will raw kaolin and spinelle kaolin be beaten with a small amount of waterglass after mist projection granulating again, atomized microball is same after high-temperature roasting Shi Hanyou spinelles kaolin, metakaolin and its minimal amount of mullite, roast after roasting microballoon crystallization through ion exchange, hydro-thermal Burning obtains the catalytic cracking catalyst containing Y type molecular sieve.

Method disclosed in CN105032472A is that crystallization control is carried out under different thermogrades, can significantly be subtracted The generation of ex situ crystallization product in few in-situ crystallization reaction.

CN103055917A will spray after catalyst filter residue, NaY molecular sieve gel, kaolin and binding agent mixed pulp and make Grain, after gained atomized microball is through gas phase crystallization, roasting, water-filling thermal crystallisation is mixed into directed agents, sodium metasilicate and NaOH, brilliant Ammonium is exchanged and roasting after rare earth exchanged at least one times at least one times to change product, and finished catalyst is obtained.

CN1549746A, CN101537368B, CN101619228B, CN103447069A, CN104209137A are also draped over one's shoulders Having revealed carries out in-situ crystallization method catalytic cracking catalyst of the preparation containing Y type molecular sieve with roasting kaolin atomized microball.

At present, the active component only Y type molecular sieve of industrialized full clay catalyst has successfully been realized both at home and abroad, it is right In increase shape selective catalysis function, production high-octane rating active component, fecund current and from now on required for catalytic cracking catalyst Low-carbon alkene function has certain limitation；Along with in-situ crystallization technical difficulty is big, production cost is high, preparation flow is long, molecule The adjustable denaturation of the universal relatively low, active component of the crystallinity and silica alumina ratio of sieve and matrix is flexible not as semi-synthesis method, thus it should There is significant limitations with effect and scope.Semi-synthetic molecular sieve catalyst is clay using binding agent (the two synthesizes matrix) It is bonded together what is be made with all types of molecular sieves.

CN1083512A discloses a kind of preparation method of the catalytic cracking catalyst comprising molecular sieve, and its method is with aluminium Colloidal sol is binding agent, and kaolin is filler, ZSM-5 molecular sieve or be active component through physics, chemically treated Y type molecular sieve Aftershaping by evenly mixing, washing, dries and is obtained.

CN1340596A discloses a kind of catalytic cracking catalyst containing super-stable Y molecular sieves, and the method contains sodium oxide molybdena Measure after carrying out rare earth exchanged for the super-stable Y molecular sieves of 3-5 weights %, with Alumina gel and/or boehmite as compound binding agent, Mix mashing with kaolin, the catalytic cracking catalyst of the weights of 5-60 containing hyperastable Y-type RE molecular sieve % is obtained.

CN103055916A with NaY molecular sieve as raw material, after carrying out ammonium exchange, hydro-thermal process, through containing H⁺、NH₄ ⁺、RE³⁺, have After the mixed solution treatment of machine solvent, spraying is obtained catalyst after being beaten with binding agent, clay.

CN103447071A with Ludox and Alumina gel as compound binding agent, molecular sieve be selected from Y-type rare earth, rare earth hydrogen Y types, One or more or they in super-stable Y molecular sieves select the mixture of type molecular sieve, beta-molecular sieve with MFI structure, mixed with clay It is spray-dried after closing mashing, finished catalyst is obtained.

CN105688977A with boehmite B and by siliceous solution modification after modified boehmite A as compound viscous Knot agent, mashing aftershaping is mixed with clay, molecular sieve and is dried, then obtain catalytic cracking catalyst after acid is exchanged or ammonium is exchanged.

CN1436835A、CN1485407A、CN1676577A、CN101451074B、CN101745416A、 It is raw material that CN101829592A, CN101829592A have also been directed to clay, binding agent, modified molecular screen, using semi-synthetic Method prepares catalytic cracking catalyst.

By the analysis to above-mentioned patent, during prior art prepares catalytic cracking catalyst, in order to reduce Have the content of the sodium oxide molybdena having a strong impact in catalyst to catalysis activity, selectivity and stability, in-situ crystallization type catalyst and Semi-synthetic molecular sieve catalyst reduces the sodium oxide content in catalyst by the way of ammonium ion exchange, and in-situ crystallization Sodium oxide molybdena is distributed in matrix and molecular sieve simultaneously in type catalyst, and for the drop sodium of catalyst increased difficulty.In order to improve The exchange degree of sodium ion, often using the method for the exchange of multiple ammonium, multiple washing and multiple intermediate calcination, and a large amount of of ammonium salt make With a large amount of generations for causing ammonia nitrogen waste water, waste gas, production cost and sewage disposal burden are increased, increased enterprise except ammonia nitrogen sets Standby input and maintenance operation cost, the in addition meeting during intermediate calcination in molecular sieve or catalyst up conversion or the ammonia nitrogen of absorption Into air, atmosphere pollution can be also caused.Therefore people require that catalytic cracking catalyst has outside more excellent catalytic performance, The ammonia and nitrogen pollution for reduce production cost, solving in catalyst preparation process is also the emphasis and difficulty of catalytic cracking catalyst exploitation Point.

CN103240113A discloses a kind of preparation method of the in-situ crystallization catalyst for reducing ammonia and nitrogen pollution, is included in spray Added during mist can with the PDDA of accumulation mode between modulation kaolin, obtain in-situ crystallization product it Afterwards, the switched environment of exchange ion, then the exchange and roasting for passing through other steps are cleared up using acid solution first, catalysis is obtained Cracking catalyst.The method can reduce more than the % of ammonium salt usage amount 15, effectively alleviate in-situ crystallization catalyst preparation process Ammonia and nitrogen pollution problem, and reduce production cost, improve the reactivity worth of catalyst.

CN100404432C discloses a kind of method for reducing ammonia and nitrogen pollution in process of zeolite modification, is included in Zeolite modifying During, with the sodium in potassium compound exchanging zeolite, then zeolite exchange modification is further carried out with ammonium salt.The method does not increase Plus Zeolite modifying cost, ammonium salt usage amount reduction by 50% or so, so that in reducing ammonia and nitrogen pollution and ammonia nitrogen waste water processing procedure Burden and investment, be a kind of environmental protection technology of modified zeolite；Prepared zeolite and catalyst, with lower oxidation Sodium content, catalyst performance is basically unchanged or increases.

CN103028431A discloses a kind of process for cleanly preparing of synthetic zeolite catalysts cracking catalyst, and the method is using normal Rule in-situ crystallization method prepares modified molecular screen or synthetic zeolite catalysts cracking catalyst, and by Crystallization of Zeolite filtrated stock and/or The ammonia nitrogen waste water that crystallization material washing water is produced with molecular sieve exchange process mixes to be washed as the spray of catalyst spray tail gas generated by granulation The spray washing liquid of tower is washed, and will acidifying aluminium salt or the above-mentioned spray recovered liquid of acid solution addition, plastic, filtering, filtrate discharge, filter residue As synthesis of molecular sieve raw material.Change method while qualified catalytic cracking catalyst product is prepared, with very low operating cost Make the ammonia-nitrogen content high that process produces waste water can direct qualified discharge, silicon compound can recycling use entirely in waste water.

Although above-mentioned each method greatly reduces the ammonia nitrogen technique waste water in catalytic cracking catalyst preparation process, but still or Ammonium ion is introduced more or less, it is impossible to is reached and is thoroughly produced without ammonification.In fact, filtrate ammonia-nitrogen content is high in ammonium exchange step Ammonia-nitrogen content also reaches 150-1500 mg/kg up in 4000-10000mg/kg, or even washings.And standard GB/T 8978- 1996《Integrated wastewater discharge standard》The ammonia nitrogen first discharge standard of middle requirement is 15mg/kg, and secondary discharge standard is 50mg/ Kg, will reach this discharge standard, certainly will increase sewage disposal burden.Therefore with new《Law on Environmental Protection》Implementation and citizen The raising of environmental consciousness, people are in the urgent need to development process is simple, the catalytic cracking catalyst of low cost, production process without ammonification New preparation technology.

CN102794191A, CN102078820A disclose a kind of new method that catalytic cracking catalyst is prepared without ammonia process, It is the mixed acid solution in low temperature, the inorganic acid of low acid concentration and organic acid that molecular sieve and catalyst exchange washing process in method In carry out, this method reduce the sodium oxide content in catalyst, it is to avoid molecular sieve exchange and catalyst detergent operation in Ammonia and nitrogen pollution, substantially reduce water consume and wastewater treatment expense.Have the disadvantage with inorganic acid and organic acid to molecular sieve and catalyst While exchanging washing drop sodium, larger is destroyed to crystal structure of molecular sieve, molecular sieve crystallinity is poor in causing catalyst, reduces The heat endurance and hydrothermal stability of catalyst.

In addition from Beyer et al. (Beyer, Belenykaja. Studies in Surface Science and Catalysis, 1980, 5:203-210) since the gaseous ion exchange process of proposition molecular sieve in 1980, using this without ammonia Method prepares low sodium super stable molecular sieve and catalytic cracking catalyst also by people's extensive concern, and its chemical reaction mechanism is：

M_1/n[AlO₂·(SiO₂)_x]+SiCl₄→1/nMCl_n+AlCl₃+[(SiO2)_x+1], wherein M is metal ion.

The essence for being not difficult to find out molecular sieve gaseous ion exchange process is will to contain silicon tetrachloride with Y type molecular sieve molecular sieve in height The lower contact of temperature, while abjection aluminium, silicon is filled on aluminium room, and the aluminium taken off is escaped in the form of aluminum chloride gas, while chlorine Change aluminium and also generate NaAlCl with the sodium effect in molecular sieve₄Double salt, then by way of washing or acid extracting, can obtain sodium content It is low, crystallization reservation degree is high, duct is unimpeded, silica alumina ratio be up to 550 Y type molecular sieve, this technique thoroughly prevented ammonia and nitrogen pollution.

In CN1840614A by one or more in dry RENaY, REHY or REY molecular sieve and silicon tetrachloride according to Silicon tetrachloride：The weight of Y type molecular sieve=0.1-0.9: 1 at 100-600 DEG C, is reacted 10 minutes to 6 hours, gas than contact Weight more than the % of Y type molecular sieve sodium oxide molybdena removing 90 after phase ion-exchange reactions, then by reacted Y type molecular sieve directly with it is viscous Knot agent, clay mixing mashing, through washing, filtering, being dried to obtain catalytic cracking catalyst finished product after spray shaping.The shortcoming of this method It is that when gaseous ion is exchanged, rare earth ion significantly can exchange Y-shaped molecular sieve containing rare earth by silicon tetrachloride, reduce Rare earth utilization rate；Directly sprayed with other raw material pulpings without washing exchange step after molecular sieve drop sodium super stabilizing simultaneously, this The harmful ion deviate from gaseous ion exchange process, such as Na can be caused⁺、NH₄ ⁺、SO₄ ^2-Ion etc. reenters molecular sieve and urges In agent.

CN104556132A discloses a kind of preparation method of high silica alumina ratio ZSM-5 molecular sieve, including by ZSM-5 molecular sieve Former powder is incorporated into the super steady reactor of gas phase, in the case where being conveyed without carrier gas, makes ZSM-5 molecular sieve original powder super steady from gas phase The molecular sieve entrance of reactor move to outlet during with silicon tetrachloride gas haptoreaction.

After obtaining NaY molecular sieve microsphere using traditional in-situ crystallization legal system in CN102553630A, then with silicon tetrachloride gas According to 0.1-0.9:1 weight at 150-500 DEG C, is reacted 10 minutes to 6 hours, reacted in-situ crystallization NaY than contact Microsphere of zeolite removes the Na of remaining in microballoon with 20-100 °C of decationizing water washing⁺、Cl^-、Al³⁺Soluble by-products, then The catalytic cracking catalyst containing high silica alumina ratio small crystal grain Y-shaped molecular sieve is obtained, but the method is still not fee from in-situ crystallization technology hardly possible Degree is big, the drawbacks such as sodium difficulty drop in production cost high, molecular sieve or catalyst.

CN102049315A、CN102049316A、CN102050459A、CN102050460A、CN102451655A、 In CN102451656A, CN102451657A, CN102451658A, CN102451729A, the gaseous ion of molecular sieve exchanges anti- Should be carried out in horizontal straight tube shape reactor, molecular sieve and gas phase silicon tetrachloride are in a tubular reactor with inert carrier gas flow Dynamic and haptoreaction, reacted molecular sieve mixes with binding agent, clay and water after decationizing water washing and is beaten and granulates, Obtain catalytic cracking catalyst.But the method carries sieve particle flowing, avoids sieve particle from blocking up to reach gas The purpose of pipeline is filled in, flow rate of carrier gas certainly will be increased, so as to cause reaction depth to be difficult to improve；In addition to it is deep to improve reaction Degree, need to increase the intake of silicon tetrachloride, inevitably enlarge the load of exhaust treatment system；And pass through to control the length of tubular reactor Spend to control time of contact, there is operational inconvenience in actual production.

In CN103769193A, CN103785436A, above-mentioned horizontal straight tube shape reactor is optimized, molecular sieve Gaseous ion exchange reaction is carried out in an inclined straight tube-like reactor, and the tubular reactor can be around body axle Line is rotated and relied in inclined tube in the case of being conveyed without carrier gas with weir plate and flight, molecular sieve and gas phase silicon tetrachloride Mechanical transmission device or gravity are moved, and molecular sieve directly mixes with matrix, water and be beaten without washing after reaction.It can be seen that In the method, the molecular sieve concentration in reactor is high, and bed density is higher, and molecular sieve is in pipeline and silicon tetrachloride is in close phase State, mass-and heat-transfer effect is poor, and the property of product can be caused to differ；In addition, silicon tetrachloride gas is not by carrier gases dilute, it is highly concentrated The silicon tetrachloride gas of degree is contacted with sieve particle, is reacted stronger and is destroyed larger to crystal formation, causes molecular sieve structure to cave in Seriously, product crystallinity declines to a great extent, and the amount of heat released cannot be taken away by carrier gas and easily produce mol sieve beds office Portion overheats；Directly mix mashing with matrix, water so that Na without washing after molecular sieve after simultaneous reactions⁺、NH₄ ⁺、SO₄ ^2-Deng Harmful ion ion is reentered in molecular sieve and catalyst；And silicon tetrachloride tail gas in the absorption tower with alkaline reaction after, Directly as waste water discharge, greatly destruction can be caused to environment.

CN103785437A, CN103785438A, CN103787352A, CN104549445A are on the basis of the above method On, increased the washing process to molecular sieve after reaction, but still have that mass-and heat-transfer effect is poor, product property differs, instead Answer the problems such as hot-spot, brine waste are in line to pollute environment.

By the analysis to above-mentioned patent, existing gaseous ion exchange process prepares semi-synthetic catalytic cracking catalyst Process, Y type molecular sieve raw material used is mainly by pre- modified various molecular sieves, such as HY, NH₄Y、REY、REHY、 RENaY, REUSY etc., rare earth ion is significantly deviate from, causes rare earth utilization rate low when there is reaction here, in addition gas Phase ion-exchange reactions is connect with the silicon tetrachloride gas being with or without by carrier gases dilute in specific Gas-phase reactor Reaction is touched, silicon tetrachloride meets hydrolysis generation silica gel and hydrochloric acid, and silica gel easily blocks pipeline, and hydrochloric acid is broken to equipment and molecular sieve It is bad very big, therefore Molecular sieve raw material need to the predrying dehydration at 400-600 DEG C before reaction.Realize that the gas phase of molecular sieve exchanges drop sodium Afterwards, molecular sieve warp or not scrubbed after reaction, then mix spray shaping after mashing with binding agent, clay, decationizing water, through washing Wash, dry after be obtained catalytic cracking catalyst.The high content of salt waste liquid that absorbs silicon tetrachloride tail gas is not given simultaneously compared with Good processing method, even directly discharges, and this can cause larger pollution to environment.

Single clay raw ore containing 20-40wt% in other traditional semi-synthetic molecular sieve type catalytic cracking catalyst --- Kaolin, this part of clay raw ore plays inert carrier, mostly without cracking activity.As crude oil heaviness increases increasingly, It is intended that carrier has certain cracking activity, it is middle decile by raw material macromolecular cleavage using the macropore or acid site of carrier Son, medium molecule enters back into molecular sieve pore passage and carries out structure selectivity cracking reaction, and it is right to improve its active effective way This part of clay raw ore is modified.

Clay raw ore is by that can obtain mesopore material of the average pore size in 4um or so after chemical modification, and the molecule of heavy oil Size is general in 3-5um, although the molecular sieve with regular crystal structure has good petrol and diesel oil selectivity, and (product structure is selected Selecting property), but mink cell focus macromolecular is difficult to carry out cracking reaction into molecular sieve crystal cage, therefore obtain new by modified Middle macropore carrier material to exploitation heavy-oil catalytic agent it is significant.In addition, chemical modification also helps reduction clay original The poisonous substance such as K, Ca, Na, Mg, Fe, Cu in ore deposit, is conducive to improving the specific surface area of clay.Other modified its surface of clay chemistry Gather the change of agglomerate form generation, groove and hole not of uniform size, these shapes can be formed on modified surface of clay Irregular surface texture causes that clay has compared with high-ratio surface and pore volume and appropriate cracking activity, to increase to heavy oil The conversion capability of macromolecular, so as to greatly improve the gasoline yield and light oil yield of catalyst, is greatly reduced hydrogen and coke Produce.On the other hand, the high conversion of heavy oil macromolecular is also advantageous to improving the total hydrogen transfer activity of catalyst.And in recent years Come very few to the research as semi-synthetic catalyst carrier, while based on reasons such as technical know-hows, relevant carrier and clay chemistry Modified condition and the report of technique are also little, it is therefore necessary to detailed research, existing hemizygous composition are compared to this Sub- sieve-type catalytic cracking catalyst preparation technology also needs to do larger Optimal improvements.

CN1044772A using single clay sepiolite after watery hydrochloric acid or nitric acid treatment as cracking catalyst carrier, but nitre Mother liquor, catalyst after acid treatment washed with sulphur ammonium after filtrate in containing a large amount of ammonia nitrogens, to environmental protection and sewage disposal cause compared with Big pressure.

It is early to be extracted with watery hydrochloric acid after the 850 DEG C of roastings of kaolin result are obtained metakaolin by CN1186105A；And urging The agent washing stage has used ammonium phosphate.

Kaolin is pressed and mixed after more than 15min is calcined at 250-500 DEG C by CN1210031A with sulfuric acid, is then washed with water Wash.

CN1388213A directly adds acid treatment 2-30min after clay is beaten to slurries, then is added in clay slurry Mist projection granulating after boehmite, waterglass, molecular sieve.Clay acid degree for the treatment of is shallower in the method, and after acid treatment without Filtering, causes the harmful metal ion extracted by acid in clay to enter in catalyst again.Water glass is added in other preparation process Glass can also cause catalyst sodium content exceeded.

CN101745412A uses inorganic alkali solution (NaOH, water glass after clay is calcined into 0.3-10h at 800-1100 DEG C One or more) processed in glass, ammoniacal liquor, sodium metaaluminate.

CN104275205A, CN104275205A, CN104276585A are mixed with the diatomite after kaolin and acid treatment Thing is carrier, and catalytic cracking catalyst is prepared using in-situ crystallization method, and repeatedly roasting or/and ammonium are exchanged period experience and rare earth is handed over Change.

Clay acid is also processed through preroast at 850-920 DEG C before modified in CN1195014A.

With the similar CN104556081A of the present invention by aqueous sulfuric acid that kaolin mass fraction is 70-98% in For carrier prepares catalyst after being processed at 150-240 DEG C.In fact, sulfuric acid concentration so high and acid treatment temperature, can be to height Ridge stone crystal structure causes greatly destruction, causes the reduction of catalyst heat endurance and hydrothermal stability (can be by its micro-activity Data are found out).Other clay is processed with such high-concentration sulfuric acid so that sulfate radical content increases by a relatively large margin in modified clay (by 0.54wt% to 0.70wt%), is likely to result in catalyst that sulfate radical is exceeded (not to disclose sulfate radical in catalyst in patent Content).

The content of the invention

Regarding to the issue above, the present invention proposes a kind of preparation method of catalytic cracking catalyst, is prepared with vapor phase method Super stable molecular sieve is active component, Compound-acid is lived, and clay is activated carrier, there is provided a kind of low without ammonia nitrogen discharge, short route, silicon high The method for preparing catalyst for being applied to catalytic cracking of sodium and high stability.

To reach above-mentioned purpose, the technical solution adopted in the present invention is, a kind of preparation method of catalytic cracking catalyst, Comprise the following steps：

A () by halogen-containing gas in the case where being conveyed with or without carrier gas, being contacted with molecular screen primary powder carries out gaseous ion friendship Reaction is changed, 100-800 DEG C of reaction temperature, reaction time 0.1-10h is obtained low-Na and high-Si aluminum ratio molecular sieve.By weight, institute The halogen-containing gas stated：Molecular screen primary powder=0.1-1:1.

B () will be obtained compound clay after not fired variety classes clay raw ore compounding, gained compound clay is through highly concentrated Degree acid treatment, is obtained acid compound clay living.

(c) in terms of catalyst butt, by step (a) gained low-Na and high-Si aluminum ratio molecular sieve 10-30wt%, step (b) gained Acid compound clay 35-65wt% and binding agent 15-35wt% living, the preferably ratio of rare earth oxide 0.1-8wt%, low-Na and high-Si aluminium Than molecular sieve 20-25wt%, acid compound clay 40-60wt% living, binding agent 20-30wt%, the ratio of rare earth oxide 1-6wt% and go Mist projection granulating after cationic water mixing mashing, fired solidification without washing, is dried, and obtains catalytic cracking catalyst finished product.

Further, described molecular screen primary powder is NaY molecular sieve original powder.

Further, the method for modifying of molecular sieve has bigger difference with prior art, and prior art prepares super stable molecular sieve institute It is mainly by pre- modified various Y type molecular sieves, such as NH with Molecular sieve raw material₄Y, HY, REY, RENaY, REHY, REUSY, And the Molecular sieve raw material made in the present invention is NaY molecular sieve original powder.

Further, the former powder of described NaY molecular sieve is once to wash former powder, that is, through mother liquor separation and once after being directly synthesized Washing gained, the NaY molecular sieve dry powder, slurries or the filter cake that are modified without chemically or physically method.

Preferably, described NaY molecular sieve original powder cell parameter 24.52~24.72, sodium oxide content 8-13wt%.

Further, described halogen-containing gas are monochloro methane (CH₃Cl, also known as methyl chloride), dichloromethane (CH₂Cl₂, and Claim METHYLENE CHLORIDE), chloroform (CHCl₃, also known as chloroform), tetrachloromethane (CCl₄, also known as carbon tetrachloride), phosphorus trichloride, pentachloro- Change phosphorus, phosphorus trifluoride, phosphorus pentafluoride, phosgene (COCl2, also known as phosgene), chloracetyl (CH3CClO, also known as chloroacetic chloride), chlorine Gas, hydrogen chloride, hydrogen bromide, fluomethane (contain CH₃F、CH₂F₂、CHF₃And CF₄), bromomethane (contain CH₃Br、CH₂Br₂、CH₂Br₃ And CBr₄), fluorine bromomethane (contain CBrF₃、CBr₂F₂、CBr₃F、CHBrF₂、CHBr₂F and CH₂BrF), fluorine chloromethane (contains CClF₃、CCl₂F₂、CCl₃F、CHClF₂、CHCl₂F and CH₂ClF), chlorine bromomethane (containing CBrCl3, CBr2Cl2, CBr3Cl, CHBrCl2, CHBr2Cl and CH2BrCl), Nitrogen trifluoride, agene, nitryl fluoride (NO₂F), nitrosyl fluoride (NOF), chloro-nitric acid (NO₂Cl), nitrosyl chloride (NOCl), boron trifluoride, boron chloride, the boron of four chlorination two, sulfur chloride (contain S₂Cl₂、SCl₂And SCl₄)、 Monochloro amine (NH₂Cl), dichlormaine (NHCl₂), three chloramines (NCl₃), methyl-monosilane (contain (CH₃)₂SiCl₂、CH₃SiCl₃、 CH₃SiHCl₂(CH₃)₃SiCl any one or a few in), preferably monochloro methane, dichloromethane, chloroform, tetrachloro Methane, phosgene, hydrogen chloride, hydrogen bromide, agene, phosphorus trichloride, phosphorus pentachloride, boron chloride, the boron of four chlorination two, monochloro amine (NH₂Cl), dichlormaine (NHCl₂), three chloramines (NCl₃), methyl-monosilane (contain (CH₃)₂SiCl₂、CH₃SiCl₃(CH₃)₃SiCl) In any one or a few, more preferably monochloro methane, dichloromethane, hydrogen chloride, phosphorus trichloride, phosphorus pentachloride, three Boron chloride, the boron of four chlorination two, methyl-monosilane (contain (CH₃)₂SiCl₂、CH₃SiCl₃(CH₃)₃SiCl in) any one or it is many Plant combination.

Further, described carrier gas be vapor, air, oxygen, hydrogen, carbon monoxide, carbon dioxide, nitric oxide, Nitrous oxide, nitrogen dioxide, nitrogen trioxide, sulfur dioxide, sulfur trioxide, carbon disulfide, hydrogen sulfide, nitrogen, argon gas, helium One or more combination in gas, monosilane, disilane.

Preferably, it is one or more in vapor, air, oxygen, carbon dioxide, nitrogen, argon gas that carrier gas is selected Combination.

In method provided by the present invention, the step（a）Middle molecular screen primary powder contacts the gas for carrying out with halogen-containing gas Phase ion-exchange reactions is temperature-programmed reaction or isothermal reaction.

Further, described temperature-programmed reaction is that molecular screen primary powder is heated into 100-400 DEG C, then with by carrier gas The halogen-containing gas contact of carrying carries out gaseous ion exchange reaction, and rises to 300- with the heating rate of 0.1-20 DEG C/min 800℃。

Further, the temperature-programmed reaction process of the molecular screen primary powder and halogen-containing gas gaseous ion exchange reaction It is：The molecular screen primary powder is heated to 100-400^oC, preferably 150-350^oC, then with the gas containing halogen carried by carrier gas Body contact carries out gaseous ion exchange reaction, and with 0.1-20^oThe heating rate of C/min, preferably 0.5-10^oC/min, rises to 350-750^oC, preferably 400-600^oC。

Further, the molecular screen primary powder is with the isothermal reaction process of halogen-containing gas gaseous ion exchange reaction：Will The molecular screen primary powder temperature maintains 100-800^oC, preferably 300-700^oAny one temperature value in C, then with by carrier gas The halogen-containing gas contact of carrying carries out gaseous ion exchange reaction.

Further, halogen-containing gas by weight：Molecular screen primary powder=0.1-1：1 weight ratio, preferably 0.3-0.8: 1, molecular screen primary powder carries out gaseous ion exchange reaction with being contacted by the halogen-containing gas that carrier gas is carried, reaction time 0.1-10h, Preferably 0.5-5h, is obtained low-Na and high-Si aluminum ratio molecular sieve.

Further, the reaction time of the gaseous ion exchange reaction is described program temperature reaction time and the constant temperature The total time that reaction time is added.

Further, a purge step is also included after the molecular screen primary powder and halogen-containing gas gaseous ion exchange reaction Suddenly.

Further, the washing step is：Molecular screen primary powder is finished after drawing off with halogen-containing gas reaction, is weighed with 5-15 times Filtered after amount, 50-80 DEG C of decationizing water mashing washing 5-120min, gained Washing of Filter Cake is extremely standby without being retained after chlorion, Without drying.

In method provided by the present invention, the step（b）Middle variety classes clay raw ore preparation method is：By kaolinite Soil, dickite, nacrite, galapectite, gangue, montmorillonite, diatomite, saponite, rectorite, pyrophyllite, illite, Hai Pao Two or more mixing in stone, attapulgite, hydrotalcite.

Further, the compound clay is kaolin, dickite, nacrite, galapectite, gangue, montmorillonite, diatom Two or more mixing in soil, rectorite, attapulgite.

Further, the clay acid before processing is processed without preroast.

Further, described acid compound clay preparation method living is：By the sour molten of compound clay and mass fraction 10-35% Liquid is sufficiently mixed at 50-100 DEG C, and it is 5-15 to control the solid mass ratio of liquid, processes 0.5-10h, filters, washs to filtrate pH=7, Without drying, acid compound clay filter cake or slurries living are obtained.

Preferably, described acid compound clay preparation method living is：By the acid of compound clay and mass fraction 15-30% Solution is sufficiently mixed at 60-90 DEG C, and it is 6-11 to control the solid mass ratio of liquid, processes 1-6h, and filtering, washing, without drying, are obtained Acid compound clay filter cake or slurries living.

Further, described acid is inorganic acid and/or organic acid.

Further, the inorganic acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and the organic acid is first One or more in acid, acetic acid, ethanedioic acid, citric acid, oxalic acid, tartaric acid.

Preferably, the acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, citric acid.

In method provided by the present invention, the step（c）Described in binding agent be original well known to those skilled in the art Material.Such as described binding agent be boehmite, Ludox, Alumina gel, phosphorus Alumina gel, phosphorus alumina gel, silica-alumina gel and it Precursor in one kind or two of which or two or more compound binding agents.

Further, described rare earth is in lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium One or more.

Preferably, the rare earth is one or more in lanthanum, cerium, praseodymium, neodymium, yttrium, scandium.

Further, the compound form of the rare earth be rare earth organic compounds, oxide, aqueous or anhydrous silicate, One or more in aqueous or anhydrous phosphoric acid salt, phosphosilicate, carbonate, iodate and chloride.

Preferably, the compound form of the rare earth is oxide, aqueous or anhydrous phosphoric acid salt, carbonate and chlorination One or more in thing.

Further, the method for the mashing, spray shaping and roasting solidification can use well known to those skilled in the art The method of mashing, spray shaping and roasting solidification.For example by described low-Na and high-Si aluminum ratio molecular sieve, acid compound clay living, glue Tie mist projection granulating after agent, rare earth are made the slurries that solid content is 30-50% in colloid generating kettle with decationizing water.For example use again Roaster carries out roasting solidification to atomized microball.

In method provided by the present invention, super-stable Y molecular sieves crystallinity obtained in described gaseous ion exchange reaction Retention rate is more than 75%, skeleton n (SiO₂)/n(Al₂O₃) it is more than 15, structure cell at least shrinks 0.2.Described catalytic cracking catalyst Sodium oxide molybdena+potassium oxide total content is less than 0.20wt% in finished product, and chloride ion content is less than 0.1wt%, and specific surface area is more than 280m²/ g。

As can be seen here, compared with prior art, the method beneficial effect for preparing catalytic cracking catalyst that the present invention is provided Major embodiment is in the following areas:

1. the method that the present invention is provided directly with NaY molecular sieve original powder as Molecular sieve raw material, is contacted into promoting the circulation of qi with halogen-containing gas Phase ion-exchange reactions, eliminates the pre- modifying processing step of Molecular sieve raw material before super stabilizing, and a step completes NaY molecular sieve original powder Drop sodium and super stabilizing, and obtained low-Na and high-Si aluminum ratio molecular sieve crystallinity retention rate, framework si-al ratio and heat endurance are equal More traditional super-stable Y molecular sieves are high.The gas phase super-stable Y molecular sieves prepared using unique gaseous ion exchange reaction, are also had There is good hydrogen transfer activity, be the excellent activity constituent element for preparing drop gasoline olefin catalyst, its high activity and high stability are also The molecular sieve content in semi-synthetic molecular sieve cracking catalyst can be reduced, Catalyst Production cost is greatly reduced.

2. the pre-dehydrating step before molecular sieve is contacted with silicon tetrachloride in the prior art is also eliminated in addition, is eliminated existing Atomized microball carries out washing, drying steps after roasting solidification in technology, greatly reduces super-stable Y molecular sieves and its catalysis is split Energy consumption (50% can be reduced), labour cost, production cycle and production cost in change catalyst preparation process.

3. intake, gaseous ion exchange reaction time and the reaction temperature of halogen-containing gas can be adjusted flexibly, carrys out modulation The sodium oxide content and silica alumina ratio of gas phase super-stable Y molecular sieves.

4. the preparation method water consumption of the catalytic cracking catalyst that the present invention is provided can reduce by 75%, significantly reduce sewage Processing load, significantly the ammonia nitrogen also from thoroughly super stable molecular sieve and catalyst preparation process has been broken away from source is dirty Dye, realizes ammonia nitrogen zero-emission.

5. the carrier in pair half synthesising cracking catalyst --- clay directly carries out high concentrated acid and is modified after compounding, breach Carry out preroast treatment in traditional sense to clay first carries out the concept of chemical modification again later.Modified compound clay has The advantage of high-ratio surface, appropriate cracking activity and low metal impurity, can be greatly lowered molecular sieve consumption in catalyst preparation, I.e. molecular sieve consumption is reduced to 20-25wt% by the 25-40wt% of prior art, and corresponding clay consumption is by prior art 20- 40wt%'s brings up to 40-60wt%, and the purpose of Catalyst Production cost is reduced so as to further function as.

6. catalytic cracking catalyst has low-Na and high-Si obtained in, can significantly reduce olefin(e) centent in gasoline, and higher is light The characteristics of oil yield, selectivity and hydrothermal stability.

In sum, NaY molecular sieve original powder is directly contacted and carries out gas phase by the method that the present invention is provided with halogen-containing gas Ion-exchange reactions a, step completes the drop sodium and super stabilizing of NaY molecular sieve original powder, and low-Na and high-Si aluminum ratio molecular sieve, the party is obtained Method processes through high concentrated acid after also variety classes clay raw ore is compounded and acid compound clay living is obtained, then with obtained low-Na and high-Si Aluminum ratio molecular sieve is active component, acid compound clay living is sprayed after mixing mashing with binding agent, rare earth, decationizing water for carrier Granulation, fired solidification without washing, is dried, and obtains catalytic cracking catalyst finished product.The catalytic cracking catalyst preparation process It is middle to have the advantages that thoroughly to be broken away from from source that ammonia and nitrogen pollution, preparation flow are extremely short, energy consumption is low, discharge of wastewater is few without ammonia nitrogen discharge, And obtained catalytic cracking catalyst has the low sodium of silicon high, the characteristics of catalysis activity higher, selectivity and life-span, can be notable Olefin(e) centent, raising light oil yield in gasoline are reduced, preventing from heavy metal pollution ability is stronger.At present, it is similar to catalytic cracking catalyst Preparation method have no report.

Specific embodiment

The method that the short route prepares catalytic cracking catalyst is further illustrated with reference to instantiation, but the present invention is simultaneously It is not limited to specific embodiment.

(1) places of origin of raw materials and specification：

1.NaY molecular screen primary powders：Moisten and the production of new catalytic material limited company in Sichuan；

2. Alumina gel：Self-control, aluminium atom content 12.2wt%, aluminium/chlorine atom compares 1.26；

3. rare earth compound：Sichuan is contained and the production of resource Holding Co., Ltd., industrial goods.

(2) analysis method in each embodiment:

1. the physical and chemical index of molecular sieve and catalyst is carried out using following means：

(1) chemical composition：Reference literature (Wang Zhanqin, Qi Guihong, Zhang Yinguang analysis and testing technologies and instrument, 2009,02:118- 123.) X fluorescence spectrum assay is used；

(2) pore volume：Reference literature (《Petrochemical Engineering Analysis method：RIPP test methods》, Yang Cui surely compile by grade, Science Press, Nineteen ninety publishes) determined using water droplet method, method is RIPP 28-90；

(3) BET specific surface area：Using low temperature nitrogen determination of adsorption method, standard is GB/T5816-1995；

(4) Y type molecular sieve crystallinity：Determined using X-ray diffraction method, standard is ASTM D3906-03 (2013)；

(5) Y type molecular sieve lattice constant：Determined using X-ray diffraction method, standard is ASTM D3942-03 (2013)；

(6) y-type zeolite n (SiO₂)/n(Al₂O₃) ratio：Reference literature (such as Huang Wei, Chu Gang, Cong Yufeng spectrographic laboratories, 2003,20(3):452-454.) determined using X-ray diffraction method.

2. the catalytic performance test of catalyst is carried out using following means：

(1) light oil micro-reactor evaluation：Commented using Beijing Torch Scientific Research Equipment Co., Ltd. TCM-2B type catalyst micro-activities Determine instrument, the standard oil general huge port light diesel fuel (235 ~ 337 DEG C of boiling range) in the country.By catalyst compressing tablet, smash, and sieve take 20 ~ 40 mesh samples, take 5.0000g and are fitted into reactor, and at 460 DEG C, the 1.5600 grams of standard oils of injection in 70 seconds are collected reacted Liquid receives oil, after cooling is weighed, carries out gas Chromatographic Simulation distillation analysis, determines liquid and receives gasoline content in oil；

Micro anti-active index (micro-activity, MA)=[1- liquid receipts oil quality × (in 1- liquid receipts oil shared by gasoline component Percentage composition)/enter standard oil quality] × 100%.

(2) fixed fluidized bed evaluation：Catalyst is advance after aging 10h under 800 DEG C, 100% steam atmosphere, in Beijing Carried out on the lucky type small fixed fluidized bed units of Green Chemistry Science and Technology Ltd. FFB- IV of Hui Er tri-.Feedstock oil is reduced pressure distillate Oily (property is shown in Table 1), 510 DEG C of reaction temperature, agent oil quality compares 5, mass space velocity 15h^-1.Oil, refinery gas are received to reacted liquid Chromatography is carried out with regenerated flue gas, the selectivity of catalyst is calculated.

The computational methods of hydrogen transfer index, conversion rate of products and selectivity are as follows：

Hydrogen transfer index=(propane yield+butane yield)/(productivity of propylene+butylene yield)；

Conversion ratio=gas yield+gasoline yield+coke yield；

Light oil yield=gasoline yield+diesel yield；

Total liquid recovery=liquefied gas yield+gasoline yield+diesel yield；

Dry gas selectivity=dry gas yied/conversion ratio；

Liquefied gas selectivity=liquefied gas yield/conversion ratio；

Gasoline selective=gasoline yield/conversion ratio；

Coke selectivity=coke yield/conversion ratio.

Embodiment 1：Take NaY molecular sieve original powder (sodium oxide content 10.3wt%, lattice constant 24.64, skeleton n (SiO₂)/ n(Al₂O₃) be 5.3, crystallinity 92%), according to halogen-containing gas phosphorus trichloride：Molecular screen primary powder=0.6：1 weight ratio, with quilt The halogen-containing gas phosphorus trichloride contact that carrier gas oxygen is carried carries out gaseous ion exchange reaction, in 530 DEG C of isothermal reaction 1h, instead Prepared low-Na and high-Si aluminum ratio molecular sieve FZS-1 after answering product scrubbed, its physical and chemical index is shown in Table 2.

Kaolin of Suzhou and Xuyi attapulgite are mixed to prepare compound clay, NT-1 is designated as, wherein in compound clay with Butt meter 80.0wt% containing Kaolin of Suzhou, the 20.0wt% of attapulgite containing Xuyi.By gained compound clay and mass fraction 15% Hydrochloric acid solution abundant pulp at 60 DEG C, it is 6 to control the solid mass ratio of liquid, processes 1h, and filtering, washing, without drying, obtain sour work Compound clay wet cake, is designated as SHNT-1.Physical and chemical index is shown in Table 3 before and after compound clay acid treatment.

In terms of catalyst butt, according to low-Na and high-Si aluminum ratio molecular sieve 20wt%, acid compound clay 55wt% living, binding agent 19wt% (wherein Alumina gel 47.4wt%；Boehmite 52.6wt%, the production of Shandong branch company of Chinese Aluminium Co., Ltd, Sodium oxide content 0.30wt%), the lanthanum chloride+lanthanum carbonate compound rare-earth compound of the 6wt% in terms of rare earth oxide (wherein lanthanum chloride： The ratio between amount of lanthanum carbonate material is 8:1) ratio, with decationizing water with solid content be 32% slurries after spray shaping, warp Roasting solidification, without washing, dries, and obtains catalytic cracking catalyst finished product, is designated as CHJ-1, its physical and chemical index and light oil micro-reactor Evaluating data is shown in Table 4.

Embodiment 2：Take NaY molecular sieve original powder (sodium oxide content 11.8wt%, lattice constant 24.67, skeleton n (SiO₂)/ n(Al₂O₃) be 5.4, crystallinity 93%), according to halogen-containing gas dichloromethane：Molecular screen primary powder=0.7：1 weight ratio, with quilt The halogen-containing gas dichloromethane contact that carrier gas vapor is carried carries out gaseous ion exchange reaction, and with the intensification of 10 DEG C/min Speed 440 DEG C are risen in 0.5h after isothermal reaction 2.5h, total reaction time 3h, prepared low-Na and high-Si after product is scrubbed Aluminum ratio molecular sieve FZS-2, its physical and chemical index is shown in Table 2.

Maoming Kaolin and Lingshou galapectite are mixed to prepare compound clay, NT-2 is designated as, with dry wherein in compound clay Base meter 60.0wt% containing Maoming Kaolin, the 40.0wt% of galapectite containing Lingshou.By gained compound clay and the sulfuric acid of mass fraction 18% Solution abundant pulp at 66 DEG C, it is 7 to control the solid mass ratio of liquid, processes 2h, and filtering, washing, without drying, obtain acid living compound Clay wet cake, is designated as SHNT-2.Physical and chemical index is shown in Table 3 before and after compound clay acid treatment.

In terms of catalyst butt, according to low-Na and high-Si aluminum ratio molecular sieve 22wt%, acid compound clay 49wt% living, binding agent 25wt% (wherein Alumina gel 28wt%；Boehmite 72wt%, Zibo Shuo Ren aluminum oxide Science and Technology Ltd. production, sodium oxide molybdena contains Amount 0.35wt%), the lanthanum chloride+cerium chloride compound rare-earth compound of the 4wt% in terms of rare earth oxide (wherein lanthanum chloride：Cerium chloride thing The ratio between amount of matter is 1:1) ratio, with decationizing water with solid content be 34% slurries after spray shaping, it is fired solid Change, without washing, dry, obtain catalytic cracking catalyst finished product, be designated as CHJ-2, its physical and chemical index and light oil micro-reactor evaluate number According to being shown in Table 4.

Embodiment 3：Take NaY molecular sieve original powder (sodium oxide content 11wt%, lattice constant 24.66, skeleton n (SiO₂)/n (Al₂O₃) be 5.4, crystallinity 92%), according to halogen-containing gas CH₃SiCl₃：Molecular screen primary powder=0.4：1 weight ratio, and is carried The halogen-containing gas CH that gas oxygen is carried₃SiCl₃Contact carries out gaseous ion exchange reaction, and with the heating rate of 3.8 DEG C/min Isothermal reaction 0.9h after 402.7 DEG C are risen in 0.45h, then 543.1 DEG C are risen to the heating rate of 0.5 DEG C/min, reaction is produced Prepared low-Na and high-Si aluminum ratio molecular sieve FZS-3 after thing is scrubbed, its physical and chemical index is shown in Table 2.

Longyan kaolin and Lingshou rectorite are mixed to prepare compound clay, NT-3 is designated as, with dry wherein in compound clay Base meter kaolin containing Longyan 94.0wt%, the 6.0wt% of rectorite containing Lingshou.By the sulfuric acid of gained compound clay and mass fraction 21%+ Phosphoric acid Compound-acid solution (wherein H in solution₂SO₄：H₃PO₄The ratio between Solute mass 0.7:1) the abundant pulp at 72 DEG C, controls liquid Gu mass ratio is 8,3h is processed, filtering, washing without drying, obtain acid compound clay wet cake living, be designated as SHNT-3.It is compound Physical and chemical index is shown in Table 3 after clay acid before processing.

In terms of catalyst butt, according to low-Na and high-Si aluminum ratio molecular sieve 24wt%, acid compound clay 41wt% living, binding agent 33wt% (wherein Alumina gel 15.2wt%；Boehmite 84.8wt%, the production of Zibo Shuo Ren aluminum oxide Science and Technology Ltd., oxidation Sodium content 0.25wt%), the lanthanum chloride+yttrium carbonate compound rare-earth compound of the 2wt% in terms of rare earth oxide (wherein lanthanum chloride：Carbonic acid The ratio between amount of yttrium material is 20:1) ratio, with decationizing water with solid content be 36% slurries after spray shaping, through roasting Baking, without washing, is dried, and obtains catalytic cracking catalyst finished product, is designated as CHJ-3, and its physical and chemical index and light oil micro-reactor are commented Valence mumber evidence is shown in Table 4.

Embodiment 4：Take NaY molecular sieve original powder (sodium oxide content 12.6wt%, lattice constant 24.69, skeleton n (SiO₂)/ n(Al₂O₃) be 5.6, crystallinity 95%), according to halogen-containing gas monochloro methane：Molecular screen primary powder=0.8：1 weight ratio, with quilt The halogen-containing gas monochloro methane contact that carrier gas vapor is carried carries out gaseous ion exchange reaction, and with the intensification of 5 DEG C/min Speed rises to 555 DEG C by 150 DEG C, and prepared low-Na and high-Si aluminum ratio molecular sieve FZS-4 after product is scrubbed, its physical and chemical index is shown in Table 2.

Wuhai kaolin, Miyi diatomite and Xishuangbanna galapectite are mixed to prepare compound clay, NT-4 is designated as, wherein The 40.0wt% of kaolin containing Wuhai in terms of butt, the 15.0wt% of diatomite containing Miyi, galapectite containing Xishuangbanna in compound clay 45.0wt%.By the hydrochloric acid of gained compound clay and mass fraction 24%+phosphoric acid Compound-acid solution (wherein HCl in solution：H₃PO₄It is molten Matter mass ratio 1:1) the abundant pulp at 78 DEG C, it is 9 to control the solid mass ratio of liquid, processes 4h, and filtering, washing, without drying, are obtained To acid compound clay wet cake living, SHNT-4 is designated as.Physical and chemical index is shown in Table 3 before and after compound clay acid treatment.

In terms of catalyst butt, according to low-Na and high-Si aluminum ratio molecular sieve 25wt%, acid compound clay 51wt% living, binding agent 23wt% (wherein Alumina gel 21.7wt%；Boehmite 78.3wt%, the production of Zibo Shuo Ren aluminum oxide Science and Technology Ltd., oxidation Sodium content 0.32wt%), the ratio of the lanthanum chloride of the 1wt% in terms of rare earth oxide, with decationizing water with solid content be 38% slurry Spray shaping after liquid, fired solidification without washing, is dried, and obtains catalytic cracking catalyst finished product, is designated as CHJ-4, its physics and chemistry Index and light oil micro-reactor evaluating data are shown in Table 4.

Embodiment 5：Take NaY molecular sieve original powder (sodium oxide content 9.1wt%, lattice constant 24.61, skeleton n (SiO₂)/n (Al₂O₃) be 5.2, crystallinity 91%), according to halogen-containing gas boron chloride：Molecular screen primary powder=0.4：1 weight ratio, and is carried The halogen-containing gas boron chloride contact that air carbon dioxide is carried carries out gaseous ion exchange reaction：In isothermal reaction at 400 DEG C After 1.5h, 451 DEG C are warming up to the heating rate of 0.1 DEG C/min, total reaction time 10h is obtained low after product is scrubbed Sodium high silica alumina ratio molecular sieve FZS-5, its physical and chemical index is shown in Table 2.

Hancheng kaolin, Xifeng attapulgite and Leiyang rectorite are mixed to prepare compound clay, NT-5 is designated as, wherein multiple Close the 73.0wt% of kaolin containing Hancheng in terms of butt, the 11.0wt% of attapulgite containing Xifeng, rectorite containing Leiyang in clay 16.0wt%.By the hydrochloric acid of gained compound clay and mass fraction 27%+acetic acid Compound-acid solution (wherein HCl in solution： CH₃The ratio between COOH Solute mass 1.5:1) the abundant pulp at 84 DEG C, it is 10 to control the solid mass ratio of liquid, processes 5h, filters, washes Wash, without drying, obtain acid compound clay wet cake living, be designated as SHNT-5.Physical and chemical index is shown in Table before and after compound clay acid treatment 3。

In terms of catalyst butt, according to low-Na and high-Si aluminum ratio molecular sieve 23wt%, acid compound clay 47wt% living, binding agent 27wt% (wherein Alumina gel 22.2wt%；Boehmite 77.8wt%, Hangzhou Zhi Huajie Science and Technology Ltd.s production, sodium oxide molybdena contains Amount 0.36wt%), the cerium chloride+lanthanum carbonate compound rare-earth compound of the 3wt% in terms of rare earth oxide (wherein cerium chloride：Lanthanum carbonate thing The ratio between amount of matter is 3:1) ratio, with decationizing water with solid content be 40% slurries after spray shaping, it is fired solid Change, without washing, dry, obtain catalytic cracking catalyst finished product, be designated as CHJ-5, its physical and chemical index and light oil micro-reactor evaluate number According to being shown in Table 4.

Embodiment 6：Take NaY molecular sieve original powder (sodium oxide content 8.4wt%, lattice constant 24.59, skeleton n (SiO₂)/n (Al₂O₃) be 5.1, crystallinity 90%), according to halogen-containing gas phosphorus pentachloride：Molecular screen primary powder=0.5：1 weight ratio, and is carried The halogen-containing gas phosphorus pentachloride contact that gas argon gas is carried carries out gaseous ion exchange reaction, after isothermal reaction 2h at 350 DEG C, 452C is risen in 1h with the heating rate of 1.7 DEG C/min, prepared low-Na and high-Si aluminum ratio molecular sieve after product is scrubbed FZS-5, its physical and chemical index is shown in Table 2.

Lingshou galapectite, Xuyi attapulgite and Linqu diatomite are mixed to prepare compound clay, NT-6 is designated as, wherein multiple Close the 92.0wt% of galapectite containing Lingshou in terms of butt, the 4.0wt% of attapulgite containing Xuyi, the 4.0wt% of diatomite containing Linqu in clay. By the formic acid of gained compound clay and mass fraction 30%+citric acid Compound-acid solution (wherein formic acid in solution：Citric acid solute Mass ratio 2.5:1) the abundant pulp at 90 DEG C, it is 11 to control the solid mass ratio of liquid, processes 6h, filters, washs, without drying, Acid compound clay wet cake living is obtained, SHNT-6 is designated as.Physical and chemical index is shown in Table 3 before and after compound clay acid treatment.

In terms of catalyst butt, according to low-Na and high-Si aluminum ratio molecular sieve 21wt%, acid compound clay 43wt% living, binding agent 31wt% (wherein Alumina gel 25.8wt%；Boehmite 74.2wt%, Henan Xing Hao new materials Science and Technology Co., Ltd., oxidation Sodium content 0.31wt%), the cerium chloride+yttrium phosphate compound rare-earth compound of the 5wt% in terms of rare earth oxide (wherein cerium chloride：Phosphoric acid The ratio between amount of yttrium material is 30:1) ratio, with decationizing water with solid content be 40% slurries after spray shaping, through roasting Baking, without washing, is dried, and obtains catalytic cracking catalyst finished product, is designated as CHJ-6, and its physical and chemical index and light oil micro-reactor are commented According to being shown in Table 4, fixed fluidized bed evaluating data is shown in Table 5 to valence mumber.

Comparative example 1：This comparative example is according to production catalytic cracking catalyst in industry well known to those skilled in the art Universal technique carries out the preparation of catalyst.By NaY molecular sieve original powder (sodium oxide content 12.6wt%, lattice constant 24.69, bone Frame n (SiO2)/n (Al₂O₃) be 5.6, crystallinity 95%) using " four hand over two to roast " technique, i.e. ammonium exchange-rare earth ion exchanged-water Vapor atmosphere roasting-rare earth ion exchanged-steam atmosphere roasting-ammonium is exchanged, then for example：With NaY molecular sieve original powder with 10 times After the mashing of weight decationizing water, according to NH₄Cl：Molecular sieve ratio=0.4：1 in 90 DEG C exchange 1h after be filtrated to get a friendship Material；After one hands over material to be beaten with 10 times of weight decationizing water, according to La₃Cl：Molecular sieve ratio=0.15：1 exchanges 1h in 90 DEG C After be filtrated to get two friendship material；Two friendships expect that 2h is calcined in 550 DEG C, 100% steam atmosphere obtains a baked material；One baked material is with 10 times After the mashing of weight decationizing water, according to La₃Cl：Molecular sieve ratio=0.15：1 in 90 DEG C exchange 1h after be filtrated to get three friendships Material；Three friendships expect that 2h is calcined in 550 DEG C, 100% steam atmosphere obtains two baked materials；Two baked materials are with 10 times of weight decationizing water After mashing, according to NH₄Cl：Molecular sieve ratio=0.2：1 filters in after 90 DEG C of exchange 1h, obtains REUSY zeolite products (note It is DBFZS-1, the molecular sieve middle rare earth counts content as 13wt% with oxide, and 2) other physical and chemical indexs are shown in Table.According still further to catalysis The REUSY molecular sieves of agent butt meter 40wt%, (Kaolin of Suzhou, is designated as DBNT-1 to the kaolin of 38wt%, and its physical and chemical index is shown in Table 3), compound binding agent (the wherein Alumina gel 30wt% of 32wt%；Boehmite 70wt%, Chinese Aluminium Co., Ltd Shandong Branch company produce, sodium oxide content 0.30wt%), with decationizing water with solid content be 35% slurries after spray shaping, system Obtain atomized microball.Gained atomized microball is in 600^oIt is scrubbed, dry after roasting solidification 1h is carried out under C, obtain catalytic cracking catalysis Agent finished product, is designated as DBCHJ-1, and its physical and chemical index and light oil micro-reactor evaluation are shown in Table 4, and fixed fluidized bed evaluating data is shown in Table 5.

Table 1

Table 2

Be can be seen that compared with comparative example by the data of table 2, prepared by the super stable molecular sieve preparation method provided using the present invention Low-Na and high-Si aluminum ratio molecular sieve sodium content is extremely low, and framework of molecular sieve silica alumina ratio is greatly improved, molecular sieve relative crystallinity retention rate Height, lattice constant is significantly shunk, and temperature failure temperature is greatly improved, and molecular sieve specific surface area also increases, and illustrates pore-creating Substantially, data above shows that a kind of low-Na and high-Si aluminum ratio molecular sieve performance of present invention offer is excellent to effect.

Table 3

Be can be seen that compared with comparative example by the data of table 3, the clay compounding and acid activation processing method provided using the present invention The harmful element contents such as acid compound clay potassium living, sodium, calcium, magnesium, the iron of preparation decline to a great extent, and its particularly important specific surface area is big Width is improved.

Table 4

Table 5

Be can be seen that compared with comparative example 1 by the data of table 4, table 5, use present invention offer exchanges legal system with gaseous ion Standby super stable molecular sieve is active component, Compound-acid is lived, and clay is activated carrier, is prepared into catalytic cracking catalyst without ammonia process, its Alkali metal content is low, and the specific surface area and pore volume of catalyst are greatly improved, and illustrates molecular sieve and carrier pore-creating effect Substantially.Light oil micro-reactor evaluating data shows that the hydrothermal stability of catalyst prepared by the present invention is also greatly improved compared with comparative example 1.

Small fixed flowing bed evaluating data shows, compared with comparative example 1, prepared by the method provided using the present invention urges Fluidized cracking catalysts, its heavy oil conversion performance is strong, and hydrogen transfer index is dramatically increased, olefin(e) centent in reduction catalytically cracked gasoline Ability is strong, and the selectivity of coke is good, and light oil yield is high.Data above shows a kind of catalytic cracking catalyst of present invention offer Catalytic cracking catalyst excellent performance prepared by preparation method.

Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair Bright preferably implementation method, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art Member can be designed that a lot of other modification and implementation methods, and these modifications and implementation method will fall in principle disclosed in the present application Within scope and spirit.

Claims (10)

1. a kind of preparation method of catalytic cracking catalyst, it is characterised in that comprise the following steps：

A () by halogen-containing gas in the case where being conveyed with or without carrier gas, being contacted with molecular screen primary powder carries out gaseous ion friendship Reaction is changed, 100-800 DEG C of reaction temperature, reaction time 0.1-10h is obtained low-Na and high-Si aluminum ratio molecular sieve, by weight, institute The halogen-containing gas stated：Molecular screen primary powder=0.1-1:1；

B () will be obtained compound clay after not fired variety classes clay raw ore compounding, by compound clay and mass fraction 10- 30% acid solution is sufficiently mixed at 50-100 DEG C, and it is 5-15 to control the solid mass ratio of liquid, processes 0.5-10h, filtering, washing, nothing Drying is needed, acid compound clay filter cake or slurries living are obtained；

C () is living by step (a) gained low-Na and high-Si aluminum ratio molecular sieve 10-30wt%, step (b) gained acid in terms of catalyst butt After compound clay 35-65wt% and binding agent 15-35wt%, the ratio of rare earth oxide 0.1-8wt% mix mashing with decationizing water Mist projection granulating, fired solidification without washing, is dried, and obtains catalytic cracking catalyst finished product.

2. the preparation method of a kind of catalytic cracking catalyst according to claim 1, it is characterised in that：Described molecular sieve Former powder is NaY molecular sieve original powder, and described NaY molecular sieve original powder is separated after being directly synthesized once to wash former powder through mother liquor With once washing gained, the NaY molecular sieve dry powder, slurries or the filter cake that are modified without chemically or physically method.

3. the preparation method of a kind of catalytic cracking catalyst according to Claims 2 or 3, it is characterised in that：Described NaY Molecular screen primary powder cell parameter 24.55~24.72, sodium oxide content 8-13wt%.

4. the preparation method of a kind of catalytic cracking catalyst according to claim 1, it is characterised in that：Wherein described contains Halogen gas is chloromethane, phosphorus trichloride, phosphorus pentachloride, phosphorus trifluoride, phosphorus pentafluoride, phosgene, chloracetyl, chlorine, chlorination Hydrogen, hydrogen bromide, fluomethane, bromomethane, fluorine bromomethane, fluorine chloromethane, chlorine bromomethane, Nitrogen trifluoride, tri-chlorination Nitrogen, nitryl fluoride, nitrosyl fluoride, chloro-nitric acid, nitrosyl chloride, boron trifluoride, boron chloride, the boron of four chlorination two, sulfur chloride, a chlorine One or more combination in amine, dichlormaine, three chloramines, methyl-monosilane.

5. the preparation method of a kind of catalytic cracking catalyst according to claim 1, it is characterised in that：Described carrier gas is Vapor, air, oxygen, hydrogen, carbon monoxide, carbon dioxide, nitric oxide, nitrous oxide, nitrogen dioxide, three oxidations two One or more combination in nitrogen, sulfur dioxide, sulfur trioxide, carbon disulfide, hydrogen sulfide, nitrogen, argon gas, helium.

6. the preparation method of a kind of catalytic cracking catalyst according to claim 1, it is characterised in that：The molecular screen primary It is temperature-programmed reaction or isothermal reaction that powder contacts the gaseous ion exchange reaction for carrying out with halogen-containing gas.

7. the preparation method of a kind of catalytic cracking catalyst according to claim 6, it is characterised in that：Described program liter Temperature reaction is that molecular screen primary powder is heated into 100-400 DEG C, then is contacted into promoting the circulation of qi with the halogen-containing gas carried by carrier gas Phase ion-exchange reactions, and rise to 300-800 DEG C with the heating rate of 0.1-20 DEG C/min.

8. the preparation method of a kind of catalytic cracking catalyst according to claim 6, it is characterised in that：Described constant temperature is anti- It is that the molecular screen primary powder is heated into 100-800 to answer process^oAny one temperature value in C, then carried with by carrier gas Halogen-containing gas contact carry out gaseous ion exchange reaction.

9. the preparation method of a kind of catalytic cracking catalyst according to claim 1, it is characterised in that：Described is not of the same race Class clay raw ore preparation method is：By kaolin, dickite, nacrite, galapectite, gangue, montmorillonite, diatomite, saponite, Two or more mixing in rectorite, pyrophyllite, illite, sepiolite, attapulgite, hydrotalcite.

10. the preparation method of a kind of catalytic cracking catalyst according to claim 1, it is characterised in that：The acid is salt One or more combination in acid, sulfuric acid, phosphoric acid, boric acid, formic acid, acetic acid, ethanedioic acid, citric acid, oxalic acid, tartaric acid.