CN103506153B - Catalytic cracking catalyst for reducing coke yield and producing gasoline - Google Patents

Abstract

The invention relates to a catalytic cracking catalyst for reducing coke yield and producing gasoline. Based on the weight of the dry base, the catalytic cracking catalyst contains 10wt%-50wt% of modified Y type molecular sieve, no more than 30wt% of specific rare earth-containing Y type molecular sieve, 10wt%-70wt% of clay and 10wt%-40w% of inorganic oxide binder based on oxide base, wherein the lattice constant of the modified Y type molecular sieve is 2.420-2.440nm; by calculating in percentage by weight, P accounts for 0.05-6%, RE2O3 accounts for 0.03-10%, aluminum oxide is less than 22%, and the specific hydroxyl nest concentration is less than 0.35mmol/g. The catalytic cracking catalyst provided by the invention can reduce green coke, improve the utilization rate of heavy oil and improve gasoline selectivity.

Description

A kind ofly reduce coke yield and produce the catalytic cracking catalyst of gasoline

Technical field

The present invention relates to a kind of hydrocarbon oil catalytic cracking catalyzer, further relate to and a kind ofly reduce coke yield and improve the catalytic cracking catalyst of gasoline selective.

Background technology

Along with the minimizing day by day of petroleum resources, petroleum heaviness, in poor quality become undisputable fact.As the main processing means by heavy oil conversion being gasoline and diesel oil light-weight fuel oil, catalytic cracking inevitably needs to process more heavy oil feedstocks more inferior.The reduction of transformation efficiency and the increase of coke yield are that stock oil heaviness in poor quality is to one of catalytic cracking performance bringing impact.Be directed to this, people from molecular sieve modified, catalyzer be fabricated onto technological design aspect carried out large quantifier elimination (Liu Tao, Zhang Zhongdong, Haitao Zhang etc. China and foreign countries energy .2009,14(1): 71-77).But current most Catalyst Design and full scale plant operation are all the high yields realizing lightweight oil and liquefied gas product by improving cracking reaction transformation efficiency, cause coke yield obviously higher, cause the waste of stock oil resource.Improve heavy oil utilization ratio, suitably can control transformation efficiency, reduce coke yield, to improve coke selectivity.In the composition of FCC catalyzer, the combined reaction performance of molecular sieve on catalyzer has conclusive impact, and therefore carrying out modification to molecular sieve is improve one of the most effective means of catalytic cracking catalyst reactivity worth.

Coke is made up of the poor hydrogen compound that various scarce hydrogen degree is different, is the product of hydrogen transfer reactions, thus will reduces coke yield, needs suitably to reduce hydrogen transfer reactions.The main process of hydrogen transfer reactions is the absorption of protonated alkene at acidic zeolite center, reaction and desorption.Molecular sieve acid site density is high, and hydrogen transfer reactions increases.The sour density of molecular sieve is relevant with its framework si-al ratio.The molecular sieve that framework si-al ratio is low, aluminum-oxygen tetrahedron acid site is many, and the sour density of molecular sieve is high, and its hydrogen transfer reactions is many, and speed is fast, and coke yield is high; And the molecular sieve of high framework si-al ratio, acid site density is low, and hydrogen transfer reactions is relatively few, and coke yield reduces.The coke selectivity that active ingredient has had to be ensured as can be seen here, active ingredient must be made to have low lattice constant, appropriate sour density.

As everyone knows, cracking unit, in operation process, for maintaining the stable of reactive behavior, needs constantly to draw off old dose, fresh makeup catalyst.Thus there is age structure in catalyzer.Its reactivity worth of the catalyzer of different ages is different.Live catalyst Middle molecule sieve structure cell is comparatively large, and cracking activity is high, and hydrogen transference ability is strong, and coke yield is high; And the catalyzer of long-term operation molecular sieve generation framework dealumination under hydrothermal conditions, structural breakdown, makes catalyst cracking activity decrease, and reaction preference is deteriorated.Obviously the catalyzer of this two states is all unfavorable for the raising of heavy oil utilization ratio.Improve catalyzer heavy oil utilization ratio, will start with from the reactivity worth of raising molecular sieve under different level of deactivation, use the molecular sieve of low unit cell dimension on the one hand, to reduce the coke selectivity of fresh molecular sieve, on the other hand, pass through modification, improve molecular sieve activity stability, to improve equilibrium activity, reduce the active difference of zeolite-water thermal ageing when different steps as far as possible, to reduce the coke selectivity of catalyzer on the whole, thus improve heavy oil utilization ratio.

Use the Y zeolite of low unit cell dimension that catalyst activity and heavy oil conversion performance must be made to decline, other modifying element must be added to improve the performance of active ingredient for this reason.Rare earth modified cracking activity and the hydrothermal stability that can significantly improve molecular sieve, but large quantity research shows, the molecular sieve coke selectivity of high rare-earth content is poor, in low content of rare earth comparatively suitable.In recent years, people adopt method of modifying phosphorus and rare earth being introduced jointly molecular sieve, to improve catalytic performance further.

CN1624079A discloses a kind of hydrocarbon cracking catalyzer containing modcfied faujasite, first the method for modifying of its mesolite for carrying out permutoid reaction by faujusite and phosphorus compound and ammonium compound, water and weight zeolite are than 2 ~ 25, pH2.0 ~ 6.5, temperature is 10 ~ 150 DEG C, swap time is 0.1 ~ 4 hour, then in exchange slurries, earth solution is introduced, reaction times is 1 ~ 60 minute, further reaction, after filtration, washing, through phosphorus and rare earth modified zeolite at 250 ~ 800 DEG C, roasting 0.1 ~ 3.5 hour under 1 ~ 100% steam and obtaining.Lattice constant 2.440 ~ the 2.465nm of the modified zeolite adopting this method of modifying to prepare, sodium oxide 2.0 ~ 6.5 % by weight, phosphorus content 0.01 ~ 3 % by weight, rare earth oxide 0.1 ~ 15 % by weight.Containing the catalyst activity good stability of this molecular sieve, yield of gasoline is high, and coke yield is low, heavy oil cracking ability and preventing from heavy metal pollution ability strong.The catalyzer adopting this modified molecular screen to prepare has higher yield of gasoline and good coke selectivity.But the molecular sieve lattice constant obtained by this preparation method is comparatively large, will affect molecular sieve catalyst coke selectivity.

CN 1506161A discloses a kind of hyperastable Y-type RE molecular sieve active ingredient, and this modified molecular screen is containing the heavy % of rare earth oxide 8 ~ 25, and phosphorus 0.1 ~ 3.0 weighs %; The heavy % of sodium oxide 0.3 ~ 2.5, degree of crystallinity 30 ~ 55%, lattice constant 2.455 ~ 2.472 nanometer.Molecular sieve take NaY zeolite as raw material, through rare earth exchanged and first time roasting, obtains " one hands over a roasting " rare earth NaY; React with rare earth, phosphorus containg substances and ammonium salt again, carry out second time calcination process, acquisition phosphorus and rare earth modified modified Y zeolite.This modified molecular screen coke yield is moderate.Molecular sieve content of rare earth obtained is by this method higher, and lattice constant is large, and molecular sieve coke selectivity is affected.

CN1317547A discloses a kind of FCC catalyzer, wherein containing a kind of phosphorus and the composite modified Y zeolite of rare earth, this molecular sieve by NaY zeolite through rare earth and ammonium salt hybrid switching again after hydrothermal calcine process, react with phosphorus compound, then the preparation of second time calcination process is carried out, wherein RE ₂o ₃the weight ratio of/Y zeolite is 0.02 ~ 0.18, and the weight ratio of ammonium salt/Y zeolite is the weight ratio of 0.1 ~ 1.0, P/Y zeolite is 0.003 ~ 0.05, maturing temperature 250 ~ 750 DEG C, water vapor condition 5 ~ 100%, 0.2 ~ 3.5 hour time.

CN 101537366A reports a kind of modified molecular screen improving coking behavior, it is characterized in that this molecular sieve hands over the preparation method of two roastings to obtain by NaY molecular sieve through two, by weight percentage, and RE ₂o ₃be 0.05 ~ 4.0%, P is 0.05 ~ 5.0%, structure cell is 2.430 ~ 2.440nm, degree of crystallinity is 35 ~ 55%.This molecular sieve have more in macropore pore volume and satisfactory stability, while reduction catalyst coke productive rate, heavy oit pyrolysis ability improves further, thus total liquid yield is improved, and is particularly conducive to the raising of yield of light oil.

EP 0421422 refer to a kind of faujusite for hydrocracking catalyst, it is characterized in that this faujusite is at wave number 3740 ± 10cm ^-1has the infrared absorption of 20% at least, at wave number 3560 ± 10cm ^-1have 5% infrared absorption at least, the former is at least 2 than the latter.This faujusite specific surface area at least 650m ²/ g, framework si-al ratio 20 ~ 50, lattice constant 24.15 ~ 23.50.

CN 1951814A discloses a kind of modified Y zeolite, and its feature is 7 ~ 30 at the silica alumina ratio of this modified Y zeolite, specific surface area 700 ~ 900m ²/ g, lattice constant 2.425 ~ 2.445nm, relative crystallinity>=80%, Na ₂o content≤0.25%, the secondary pore of 1.7 ~ 10nm accounts for more than 45% of total pore volume, and non-framework aluminum accounts for more than 30% of whole alumiunum amount, infrared acidity 0.15 ~ 0.55mmol/g.This modified zeolite take NaY as raw material, obtains through the process such as ammonium exchange, hydrothermal treatment consists, de-non-framework aluminum, reaming, intermediate water thermal treatment.Modified zeolite can as the acidic components of various catalyzer, as middle oil type hydrocracking catalyst.

Several sections of patent documentations improve the silica alumina ratio of Y zeolite by the method for hydrothermal dealumination and (or) chemical dealuminization above, through intermediate water thermal bake-out to realize the contraction of structure cell, but at deep sealumination modified (SiO ₂/ Al ₂o ₃mol ratio>=15) often cause zeolite structured destruction in process, zeolite crystallinity is declined.

US 5013699 proposes a kind for the treatment of process of Y zeolite, is by NaY zeolite through ammonium ion exchange, then carries out high-temperature vapor process, and sample carries out ammonium exchange again and removes aluminium under the condition of PH < 4, obtains zeolite product.This treatment process adopts and processes zeolite sample at the low ph, and does not adopt sfgd., easily causes zeolite framework to destroy, zeolite crystallinity is reduced.

US 4503023 discloses a kind of LZ ~ 210 zeolite and preparation method thereof, NaY zeolite silicofluoride is carried out dealumination complement silicon to improve the silica alumina ratio of zeolite, the product degree of crystallinity obtained is higher, but when adopting silicofluoride to carry out dealuminzation to Y zeolite, the SiO of zeolite product ₂/ Al ₂o ₃mol ratio usually can not higher than 13, otherwise the degree of crystallinity of zeolite product will significantly decline.In addition, the modified Y zeolite secondary pore adopting the silicofluoride method of carrying out dealumination complement silicon to prepare is few, is disadvantageous for being used as heavy oil catalytic cracking reaction.

Summary of the invention

The object of this invention is to provide a kind of catalytic cracking catalyst of voluminous gasoline, the phosphorus containing a kind of " three hand over three roastings " in this catalyzer and rare earth modified Y zeolite, can improve gasoline selective, reduce coke yield.

The invention provides a kind of catalytic cracking catalyst reducing coke yield high-yield diesel oil, containing in the Modified Zeolite Y of butt 10 % by weight ~ 50 % by weight, to be no more than in butt 30 % by weight the specific Y zeolite containing rare earth, in the clay of butt 10 % by weight ~ 70 % by weight with the inorganic oxide binder of oxide basis 10 weight ~ 40 % by weight; Described Modified Zeolite Y, lattice constant is 2.420 ~ 2.440nm, and by weight percentage, P is 0.05% ~ 6%, RE ₂o ₃be 0.03% ~ 10%, aluminum oxide is less than 22%, is less than 0.35mmol/g than hydroxyl nest concentration, described

In formula, M _{200 DEG C}, M _{500 DEG C}and M _{800 DEG C}represent respectively sample temperature 200 DEG C, 500 DEG C and 800 DEG C time the percent weight loss that records, C is sample crystallinity;

The described specific Y zeolite containing rare earth be rare earth modified gas phase super-stable Y molecular sieves and/or containing rare earth through acid-treated hydrothermal dealumination Y zeolite.

The preparation method of described catalytic cracking catalyst, the method comprises the Modified Zeolite Y described in preparation, and prepared Modified Zeolite Y, the described specific Y zeolite containing rare earth, clay and inorganic oxide binder are mixed making beating, spray-dired step;

Described Modified Zeolite Y (also claiming is phosphorous and Modified Zeolite Y that is rare earth) can (be hand over the preparation methods of three roastings through three and obtain, so-called " three hand over three roastings " is the general abbreviation of this area to a kind of molecular sieve modified technique, refer to NaY molecular sieve to be raw material, adopt the combination modified technique of three exchanges and three hydrothermal treatment consists, rare earth and phosphorus adopt exchanged form, add phosphorous exchange solution and exchange containing rare earth exchanged solution, phosphorus can add in arbitrary exchange operation, can once or several times add, rare earth can add in arbitrary exchange operation beyond a friendship, exchange operation and also can add removing of dealumination agent promotion aluminium, chemical dealuminization process can be carried out in arbitrary exchange operation beyond a friendship.Filter after exchanging, washing is conventional method.

Described catalytic cracking catalyst of the present invention can show satisfactory stability in catalytic cracking process, for heavy oil fluid catalytic cracking, can reduce green coke, improves gasoline selective, improves heavy oil utilization ratio.

Accompanying drawing explanation

The crystallinity data comparison curves of Fig. 1 embodiment and comparative example.

The crystallization of Fig. 2 embodiment and comparative example retains degrees of data comparison curves.

The activity data comparison curves of Fig. 3 embodiment and comparative example.

The coke selectivity data comparison curves of Fig. 4 embodiment and comparative example.

Embodiment

Modified Zeolite Y of the present invention is phosphorous and Modified Zeolite Y that is rare earth, obtained by the preparation method of NaY molecular sieve through " three hand over three roastings ", its born of the same parents' constant is 2.420 ~ 2.440nm, preferably lattice constant is 2.428 ~ 2.438nm, by weight percentage, P is 0.05 ~ 6%, is preferably 0.1 ~ 4.5%, RE ₂o ₃be 0.03 ~ 10%, be preferably 0.1 ~ 4.5%, aluminum oxide is less than 22%, is generally 10-22%, is preferably less than 20%, is less than 0.35mmol/g than hydroxyl nest concentration, such as, be 0.01mmol/ ~ 0.35mmol/g, be preferably less than 0.3mmol/g, described

In formula, M _{200 DEG C}, M _{500 DEG C}and M _{800 DEG C}represent respectively sample temperature 200 DEG C, 500 DEG C and 800 DEG C time the percent weight loss that records, C is sample crystallinity.

Zeolite molecular sieve framework dealumination, formed in its aluminium room " the hydroxyl nest " that be made up of four adjacent Si-OH, be the rejected region in zeolite molecular sieve lattice, its quantity and zeolite structured stability have direct relation." hydroxyl nest " quantity is more, and illustrate that the aluminium room because of framework dealumination formation on molecular sieve is more, the structural stability of molecular sieve is poorer.The aluminium room that Y zeolite is formed in hydro-thermal or chemical dealuminization process is filled by the silicon dissociated, in the modifying process of molecular sieve, dealumination process and treatment condition directly have influence on the stability of modified molecular screen, contriver is on the basis of great many of experiments, be surprised to find that the Modified Zeolite Y after " three hand over three roastings ", the aluminium room that framework dealumination is formed can fully be filled by silicon, hydroxyl nest quantity reduces, and therefore stability improves greatly.

In modified Y molecular sieve of the present invention, than hydroxyl nest concentration adopt document (Liu Xingyun, Liu Hui, Li Xuanwen etc. Acta PhySico-Chimica Sinica .1998,14 (12): 1094 ~ 1097) method that provides characterizes.This characterizing method sample is carried out thermogravimetric analysis calculate.

On weight-loss curve, less than the 200 DEG C weightlessness corresponding to desorption attached water, 200 DEG C ~ 500 DEG C correspond to the weightlessness that zeolite takes off ammonium and the dehydration of hydroxyl nest, 500 DEG C ~ 800 DEG C weightlessness corresponding to dehydroxylation.NH4 on Y zeolite ⁺decompose and just produce acid hydroxy group, therefore the mole number of hydroxyl is corresponding with NH3.After calculating hydroxyl moles by 500 DEG C ~ 800 DEG C weight-loss curves like this, be converted into NH ₃quality, then from the weight loss that 200 DEG C ~ 500 DEG C weight-loss curves calculate deduct NH3 amount, just can calculate the mole number of hydroxyl nest.

In the calculating of hydroxyl nest concentration, hydroxyl nest disappears because de-two molecular waters, therefore its molar weight is 36, two hydroxyls takes off a part water, therefore its molar weight is 9.

The preparation method of above-mentioned Modified Zeolite Y, take NaY molecular sieve as raw material, preparation process through " three hand over three roastings " obtains, so-called " three hand over three roastings " is the general abbreviation of this area to a kind of molecular sieve modified technique, namely the combination modified technique of three exchanges and three hydrothermal treatment consists is adopted, rare earth and phosphorus adopt exchanged form, add phosphorous exchange solution and exchange containing rare earth exchanged solution, phosphorus can add in arbitrary exchange operation, can once or several times add, rare earth can add in arbitrary exchange operation beyond a friendship, exchange operation also can add dealumination agent and carry out chemical dealuminization to promote removing of aluminium, chemical dealuminization process can be carried out in arbitrary exchange operation beyond a friendship.

Phosphorus containg substances in phosphorous exchange liquid of the present invention be selected from ortho-phosphoric acid, phosphorous acid, tetra-sodium, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, aluminum phosphate one or more.

In described ammonium solution containing ammonium material be selected from ammonium chloride, ammonium nitrate, volatile salt, bicarbonate of ammonia, ammonium oxalate, ammonium sulfate, monoammonium sulfate one or more.

Described containing in rare earth exchanged liquid containing rare-earth substance be selected from lanthanum trioxide, cerium oxide, lanthanum nitrate, cerous nitrate, Lanthanum trichloride, Cerium II Chloride, nitric acid mishmetal, chlorination mishmetal one or more.

The mineral acid that described adjustment exchanges liquid pH value be selected from hydrochloric acid, sulfuric acid, nitric acid one or more.

Described dealumination agent is selected from organic acid (comprising ethylenediamine tetraacetic acid (EDTA), oxalic acid, citric acid, sulphosalicylic acid), mineral acid (comprising silicofluoric acid, hydrochloric acid, sulfuric acid, nitric acid), organic and inorganic salt (comprising ammonium oxalate, Neutral ammonium fluoride, ammonium silicofluoride, ammonium borofluoride).

A kind of preparation process of preferred Modified Zeolite Y can be comprise the steps:

1) NaY zeolite and ammonium salt, phosphorus ammonium salt and water are according to NaY molecular sieve: ammonium salt: phosphorus ammonium salt: the part by weight of water=1:0.4 ~ 1.0:0 ~ 0.04:5 ~ 10 is mixed to get slurries, be 3.0 ~ 4.5 by the pH value of mineral acid adjusting slurry, then at 70 DEG C ~ 95 DEG C, at least 0.5h is processed, wash after usual 0.5 ~ 10 hour, wherein, NaY molecular sieve is in butt, and phosphorus ammonium salt is in elemental phosphorous; Described phosphorus ammonium salt is phosphorous ammonium salt, such as, in ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium pyrophosphate, ammonium phosphite one or more;

2) product step 1) obtained is roasting at least 0.5h under temperature 350 DEG C ~ 650 DEG C, 1% ~ 100% steam atmosphere, usual 0.5 ~ 10 hour, preferably within 2 ~ 6 hours, obtains a roasting molecular sieve;

3) by step 2) obtain one roasting molecular sieve roast molecular sieve with phosphoric acid, dealumination agent according to one: phosphoric acid: dealumination agent: the part by weight of water=1:0 ~ 0.04:0.02 ~ 0.3:5 ~ 10 mixes, with mineral acid adjust pH 2.4 ~ 3.5, then at 50 DEG C ~ 90 DEG C, at least 0.5 hour is processed, usual 0.5 ~ 10 hour, filter, wash, washing water temperature >=50 DEG C, be generally 50 ~ 95 DEG C, wherein, a roasting molecular sieve is in butt, and phosphoric acid is in elemental phosphorous.

4) product step 3) obtained is temperature 350 DEG C ~ 650 DEG C, and roasting at least 0.5h under 1% ~ 100% steam atmosphere, usual 0.5 ~ 10 hour, preferably obtains two roasting molecular sieves for 2 ~ 6 hours;

5) two roasting molecular sieves step 4) obtained roast molecular sieve with rare earth chloride and water according to two: rare earth chloride: the part by weight of water=1:0.01 ~ 0.05:5 ~ 10 mixes, then at 70 DEG C ~ 90 DEG C, at least 0.5 hour is processed, usual 0.5 ~ 10 hour, filter; Washing, washing water temperature>=50 DEG C, are generally 50 ~ 95 DEG C, and wherein, two roasting molecular sieves are in butt, and rare earth chloride is with RE ₂o ₃meter;

6) product step 5) obtained, at 350 DEG C ~ 650 DEG C, roasting at least 0.5h under 1% ~ 100% steam atmosphere, usual 0.5 ~ 10 hour, preferably obtains Modified Zeolite Y in 2 ~ 6 hours.

According to catalyzer of the present invention, the wherein said specific Y zeolite content containing rare earth, for being no more than 30 % by weight, is preferably 2 ~ 28 % by weight.

According to catalyzer of the present invention, the wherein said specific Y zeolite containing rare earth is the second Y zeolite and/or the 3rd Y zeolite, wherein:

Described second Y zeolite is the gas phase super-stable Y molecular sieves containing rare earth, its preparation method comprises: under agitation, Y zeolite containing rare earth is contacted with silicon tetrachloride, the temperature of contact is 100-500 DEG C, the time of contact is 0.1-10 hour, and described is 1:0.05-0.5 containing the Y zeolite of rare earth and the weight ratio of silicon tetrachloride.The concrete preparation method of described second Y zeolite can with reference to patent CN1286721C, particularly embodiment 5,6 and 8 wherein; Preferably the content of described second Y zeolite is no more than 15 % by weight.

The 3rd described Y zeolite is the acid-treated hydro-thermal super-stable Y molecular sieves containing rare earth, its preparation method comprises: be that the acid solution of 0.01-2N fully mixes at 20-100 DEG C with the ratio of liquid-solid ratio (weight) 4-20 by super-stable Y molecular sieves and concentration, process washing after 10-300 minute, filter, add rare earths salt again and carry out rare earth ion exchanged, carry out successively after exchange washing, filtering and drying.The concrete preparation method of described 3rd Y zeolite can with reference to patent CN100497175C, particularly embodiment 1-6 wherein.

Preferably, the described specific Y zeolite containing rare earth is described 3rd Y zeolite, and its content is preferably 10 ~ 30 % by weight.

Also can containing except described Modified Zeolite Y and described specific containing other molecular sieve except the Y zeolite of rare earth in catalyzer prepared by the present invention, one or more of other Y zeolite conventional in other molecular screening catalytic cracking catalyzer described, the molecular sieve with MFI structure, Beta molecular sieve, non-zeolite molecular sieve.One or more in other described Y zeolite such as REY molecular sieve, USY molecular sieve, HY molecular sieve, DASY molecular sieve, REHY molecular sieve; The described molecular sieves with MFI structure is as one or more in ZSM-5, ZRP, ZSP molecular sieve; One or more in described non-zeolite molecular sieve such as SAPO, HTS.The content of other molecular sieve described is preferably more than 10 % by weight.

Catalytic cracking catalyst provided by the invention, containing in the described Modified Zeolite Y of butt 10 % by weight-50 % by weight, to be no more than in butt 30 % by weight the specific Y zeolite containing rare earth, in the clay of butt 10 % by weight-70 % by weight with the inorganic oxide binder of oxide basis 10 % by weight-40 % by weight.The content of the described specific Y zeolite containing rare earth is preferably 0.5-30 % by weight, is more preferably 2 ~ 25 % by weight.Preferably, the described Modified Zeolite Y of 15 ~ 35 % by weight is contained in described catalytic cracking catalyst, in the DASY molecular sieve of butt 2 ~ 10 % by weight.

According to catalyzer of the present invention, wherein said clay is selected from as one or more in the clay of cracking catalyst component, such as, in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite one or more.These clays are that those of ordinary skill in the art are known.

Binding agent of the present invention is one or more in the inorganic oxide binder commonly used of catalytic cracking catalyst, preferential oxidation al binder, described alumina binder is selected from one or more in the aluminum oxide of usual the used various forms of cracking catalyst, hydrated aluminum oxide and Alumina gel.Such as, be selected from one or more in gama-alumina, η-aluminum oxide, θ-aluminum oxide, χ-aluminum oxide, pseudo-boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite), the double aluminium binder of preferred pseudo-boehmite and Alumina gel.

Catalyzer of the present invention can be prepared according to the preparation method of any existing cracking catalyst, such as by clay, molecular sieve, alumina binder mixing making beating, spraying dry and washing, filtration, dry step, these methods have detailed description in patent CN1098130A, CN1362472A, CN1727442A, CN1132898C, CN1727445A, quote as a reference in the lump here.

Spraying dry, washing, drying are prior art, and the present invention does not have particular requirement.

The following examples will be further described the present invention, but content not thereby limiting the invention.

In embodiment and comparative example, raw material specification used is as follows:

NaY molecular sieve, industrial goods, silica alumina ratio > 4.7, degree of crystallinity > 85%

Mixed chlorinated rare earth, technical grade

Ammonium sulfate, chemical pure

Phosphoric acid, chemical pure

Primary ammonium phosphate, chemical pure

Sulfuric acid, chemical pure

Oxalic acid, solid, chemical pure

Silicofluoric acid, technical grade

Hydrochloric acid, chemical pure

Second is obtained according to the method for embodiment in patent CN1286721C 5 containing the Y zeolite (Z2) of rare earth;

3rd is obtained according to the method for patent CN100497175C embodiment 1 containing the Y zeolite (Z3) of rare earth;

DASY-2.0 molecular sieve is catalyzer asphalt in Shenli Refinery of China Petrochemical Industry commercially available prod

Alumina gel is the commercial goods of catalyzer asphalt in Shenli Refinery of China Petrochemical Industry, Al ₂o ₃content is 21.5 % by weight;

Kaolin is the commercial goods of Suzhou China Kaolin Co., Ltd, solid content 78 % by weight;

Pseudo-boehmite is the commercial goods of Shandong Aluminum Plant, solid content 60 % by weight;

In embodiment and comparative example, analysis test method used is as follows:

Constituent content is by x-ray fluorescence spectrometry.

Lattice constant, degree of crystallinity by X-ray diffraction method (XRD) adopt respectively RIPP145-90 and RIPP146-90 standard method (see " Petrochemical Engineering Analysis method (RIPP test method) ", Yang Cuiding etc., Science Press, nineteen ninety version) measure.

Than in the concentration determination of hydroxyl nest, the thermogravimetric analysis data of sample adopts hereinbefore described thermogravimetric method to measure.

Catalytic cracking catalyst micro-activity (MA) measures with reference to RIPP 92-90 standard method.

What embodiment and the usage ratio described in comparative example did not have a specified otherwise is weight ratio.

Described sour aluminum ratio be concentration 36 % by weight hydrochloric acid with in the weight ratio of the pseudo-boehmite of aluminum oxide.

Embodiment 1

(1) preparation of modified molecular screen

Be that raw material ammoniumsulphate soln exchanges with NaY molecular sieve, treatment condition are: NaY molecular sieve (butt): ammonium sulfate: water=1:1.0:8(weight ratio), sulfuric acid adjust pH 3.5,85 DEG C exchanges 1h, washing.Hydrothermal calcine process, maturing temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one containing rare earth, treatment condition are: roasting molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.042:8(weight ratio), 70 DEG C exchange 1h, deionized water wash.Hydrothermal calcine process, maturing temperature 580 DEG C, 100% steam roasting time 2h.Rear sample is roasted by the solution-treated two of phosphoric acid and oxalic acid, treatment condition are: two roastings molecular sieve (butt): phosphoric acid (by P): oxalic acid (containing two molecular crystal water): water=1:0.014:0.14:8(weight ratio), with sulfuric acid adjust pH 2.8,70 DEG C process 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 550 DEG C, 70% steam roasting time 2h, obtain modified molecular screen, be designated as A1, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with deionized water in the pseudo-boehmite of 20 weight parts of aluminum oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio (described sour aluminum ratio be concentration 36 % by weight hydrochloric acid with in the weight ratio of the pseudo-boehmite of aluminum oxide, lower same) be 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 30 parts by weight kaolin clay of butt (solid content 45 % by weight, lower same), in the Alumina gel (Al of 10 weight parts of aluminum oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A1 molecular sieve of 35 weight parts of butt, in the Z2 molecular sieve of butt 5 weight part the Y zeolite of rare earth (second containing) afterwards more wherein, continue stirring 30 minutes, obtaining solid content is 30 % by weight slurries, and spraying dry makes microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄solution washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10 weight ratio) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C1 after filtration at 120 DEG C.

Comparative example 1

(1) preparation of modified molecular screen

Modified Y molecular sieve is prepared according to the method for patent CN 101537366A.

Get 100 grams of (butt) NaY molecular sieve, pour into and 1000g exchange solution is housed (containing (NH4) of 0.63% ₂hPO ₄salt and 8.58% NH ₄cl) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=3.0 ~ 3.5 simultaneously, filter after exchanging, washing; 730 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1200g is housed exchanges solution (containing the RECl of 0.58% ₃with 6.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 730 DEG C, 70% steam exist under roasting 2h, obtained modified molecular screen, be designated as B1, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 1, difference is, replaces described modified molecular screen A1 with described modified molecular screen B1, thus obtained catalytic cracking catalyst DC1.

Embodiment 2

(1) preparation of modified molecular screen

Be that raw material ammonium chloride solution exchanges with NaY molecular sieve, treatment condition are: NaY molecular sieve (butt): ammonium chloride: water=1:0.8:8, and hydrochloric acid adjust pH 4.0,90 DEG C exchanges 1h, washing.Hydrothermal calcine process, maturing temperature 550 DEG C, 80% steam roasting time 2h.Roast rear sample with phosphoric acid and silicate fluoride solution process one, treatment condition are: roasting molecular sieve (butt): phosphoric acid (by P): silicofluoric acid: water=1:0.01:0.03:8, and hydrochloric acid adjusts pH2.8, and 70 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 550 DEG C, 70% steam roasting time 2h.Roast rear sample by the solution-treated two containing rare earth, treatment condition are: two roastings molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.03:8,70 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 550 DEG C, 100% steam roasting time 2h, obtain modified molecular screen, be designated as A2, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with deionized water in the pseudo-boehmite of 20 weight parts of aluminum oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 30 parts by weight kaolin clay of butt (solid content 45 % by weight, lower same), in the Alumina gel (Al of 10 weight parts of aluminum oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described A2 molecular sieve of 25 weight parts of butt, the Z2 molecular sieve of 13 weight parts and the Z3 molecular sieve of 2 weight parts afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄solution washing ((NH ₄) ₂sO ₄solution: microspherical catalyst: H ₂o=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C2 after filtration at 120 DEG C.

Comparative example 2

(1) preparation of modified molecular screen

Modified Y molecular sieve is prepared according to the method for patent CN 101537366A.

Get 100 grams of (butt) NaY molecular sieve, pour into and 900g exchange solution is housed (containing (NH of 0.45 % by weight ₄) ₂hPO ₄salt and 10 % by weight (NH ₄) ₂sO ₄) reactor in, exchange 1h at 90 DEG C, simultaneously in exchange process, control pH value of solution=3.0 ~ 3.5, filter after exchanging, washing; 730 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1200g is housed exchanges solution (containing the RECl of 0.44 % by weight ₃with 7.8 % by weight NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 730 DEG C, 100% steam exist under roasting 2h, obtained modified molecular screen, be designated as B2, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 2, difference is, replaces described modified molecular screen A2 with described modified molecular screen B2, thus obtained catalytic cracking catalyst DC2.

Embodiment 3

(1) preparation of modified molecular screen

Be that raw material ammoniumsulphate soln exchanges with NaY molecular sieve, treatment condition are: NaY molecular sieve (butt): ammonium sulfate: water=1:1.0:10, and sulfuric acid adjust pH 3.5,90 DEG C exchanges 2h, washing.Hydrothermal calcine process, maturing temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one of phosphate-containing and oxalic acid, treatment condition are: roasting molecular sieve (butt): Secondary ammonium phosphate (by P): oxalic acid: water=1:0.018:0.03:8, and hydrochloric acid adjusts pH=3.0, and 70 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 550 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated two containing rare earth, treatment condition are: two roastings molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.02:8.0,85 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 580 DEG C, 100% water steams roasting time 2h, and obtain modified molecular screen, be designated as A3, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with a certain amount of deionized water in the pseudo-boehmite of 20 weight parts of aluminum oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 30 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight parts of aluminum oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the Z3 molecular sieve of the described A3 molecular sieve of 15 weight parts of butt, 25 weight parts afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C3 after filtration at 120 DEG C.

Comparative example 3

(1) preparation of modified molecular screen

Modified Y molecular sieve is prepared according to the method for patent CN 101537366A.

Get 100 grams of (butt) NaY molecular sieve, pour into and 1000g exchange solution is housed (containing (NH of 0.63% ₄) ₂hPO ₄salt and 10% (NH ₄) ₂sO ₄) reactor in, exchange 1h at 90 DEG C, simultaneously in exchange process, control pH value of solution=3.0 ~ 3.5, filter after exchanging, washing; 670 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 400g is housed exchanges solution (containing the RECl of 0.60% ₃with 6.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 700 DEG C, 100% steam exist under roasting 2h, obtained modified molecular screen, be designated as B3, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 3, difference is, replaces described modified molecular screen A3 with described modified molecular screen B3, thus obtained catalytic cracking catalyst DC3.

Embodiment 4

(1) preparation of modified molecular screen

Be that raw material ammonium phosphate and ammoniumsulphate soln exchange with NaY molecular sieve, treatment condition are: NaY molecular sieve (butt): primary ammonium phosphate (by P): ammonium sulfate: water=1:0.05:1.0:8, and sulfuric acid adjust pH 3.0,85 DEG C exchanges 1h, washing.Hydrothermal calcine process, maturing temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one containing oxalic acid, treatment condition are: roasting molecular sieve (butt): oxalic acid: water=1:0.15:0.020:8, and 70 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 550 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated two containing rare earth, treatment condition are: two roastings molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.01:8,70 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 600 DEG C, 100% steam roasting time 2h, obtain modified molecular screen, be designated as A4, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with a certain amount of deionized water in the pseudo-boehmite of 20 weight parts of aluminum oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 28 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight parts of aluminum oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described modified molecular screen A4 of 40 weight parts of butt, 2 weight part Z2 molecular sieves afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C4 after filtration at 120 DEG C.

Comparative example 4

(1) preparation of modified molecular screen

Modified Y molecular sieve is prepared according to the method for patent CN 101537366A.

Get 100 grams of (butt) NaY molecular sieve, pour into and 1200g exchange solution is housed (containing (NH of 1.22% ₄) ₂hPO ₄salt and 8.58% NH ₄cl) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=5.0-5.5 simultaneously, filter after exchanging, washing; 620 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1200g is housed exchanges solution (containing the RECl of 0.055% ₃with 7.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 700 DEG C, 100% steam exist under roasting 2h, obtained modified molecular screen, be designated as B4, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 4, difference is, replaces described modified molecular screen A4 with described modified molecular screen B4, thus obtained catalytic cracking catalyst DC4.

Embodiment 5

(1) preparation of modified molecular screen

Be that raw material ammonium phosphate and ammoniumsulphate soln exchange with NaY molecular sieve, treatment condition are: NaY molecular sieve (butt): primary ammonium phosphate (by P): ammonium sulfate: water=1:0.05:1.0:8, sulfuric acid adjust pH 3.5,90 DEG C exchanges 2h, washing.Hydrothermal calcine process, maturing temperature 550 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated one containing rare earth, treatment condition are: roasting molecular sieve (butt): rare earth chloride is (by RE ₂o ₃meter): water=1:0.02:8.0, hydrochloric acid adjusts pH2.9, and 85 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 580 DEG C, 100% steam roasting time 2h.Roast rear sample by the solution-treated two of phosphate-containing and silicofluoric acid, treatment condition are: two roastings molecular sieve (butt): Secondary ammonium phosphate (by P): silicofluoric acid: water=1:0.006:0.03:8, and hydrochloric acid adjusts pH=3.0, and 70 DEG C exchange 1h, filter; Deionized water wash.Hydrothermal calcine process, maturing temperature 550 DEG C, 100% water steams roasting time 2h, and obtain modified molecular screen, be designated as A5, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Pull an oar mixing with a certain amount of deionized water in the pseudo-boehmite of 20 weight parts of aluminum oxide, and in the slurries obtained, add the hydrochloric acid peptization that concentration is 36 % by weight, acid aluminum ratio is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the slurries of 30 parts by weight kaolin clay of butt, in the Alumina gel (Al of 10 weight parts of aluminum oxide ₂o ₃content is 21.5 % by weight), stir 20 minutes, add in the described modified molecular screen A5 of 5 weight parts of butt, the Z3 molecular sieve of 30 weight parts and the DASY-2.0 molecular sieve of 5 weight parts afterwards more wherein, continue to stir rear spraying dry and make microspherical catalyst.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then with (NH at 60 DEG C ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.04:1:10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, dries, obtain catalytic cracking catalyst C5 after filtration at 120 DEG C.

Comparative example 5

(1) preparation of modified molecular screen

Modified Y molecular sieve is prepared according to the method for patent CN 101537366A.

Get 100 grams of (butt) NaY molecular sieve, pour into and 1500g exchange solution is housed (containing (NH of 1.11% ₄) ₂hPO ₄salt and 8.58% NH ₄cl) in reactor, exchange 1h at 90 DEG C, in exchange process, control pH value of solution=4.5-5.0 simultaneously, filter after exchanging, washing; 650 DEG C, 100% steam exist under after roasting 2h, calcining matter is poured into and 1000g is housed exchanges solution (containing the RECl of 0.35% ₃with 7.8% NH ₄cl salt) reactor in, exchange 1h at 90 DEG C, and control pH value of solution=6.0 ~ 6.5 in exchange process, filter after exchanging, washing, 700 DEG C, 70% steam exist under roasting 2h, obtained modified molecular screen, be designated as B5, physico-chemical property characterization result lists in table 1.

(2) preparation of catalytic cracking catalyst

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 5, difference is, replaces described modified molecular screen A5 with described modified molecular screen B5, thus obtained catalytic cracking catalyst DC5.

Comparative example 6

Prepare catalytic cracking catalyst according to the method for embodiment 1, replace the A1 molecular sieve in embodiment 1 with the Z3 molecular sieve of equivalent, be designated as DC6.

Table 1

Test case 1

This test case illustrates the cracking reaction performance adopting catalytic cracking catalyst of the present invention.

By above-mentioned catalytic cracking catalyst C1-C5 and DC1-DC6, at 800 DEG C, under 100% water vapor condition aging 8 hours, the reactivity worth of catalyzer is evaluated, catalyst filling amount 9g by small fixed flowing bed ACE R+ device (being manufactured by U.S. Kayser Technology Inc. company designs).At temperature of reaction 518 DEG C, air speed 16h ^-1, agent-oil ratio (weight) is under the condition of 5.5, using the catalytic mixing oil shown in table 2 as stock oil, inject described ACE R+ device and carry out catalytic cracking reaction, result is as shown in table 3.

Table 2

Density, g/cm 3(20℃)	0.8994
		Viscosity (100C), mm 2/s	5.63
Condensation point, DEG C	34
		Carbon residue, % by weight	0.25
Constituent content, % by weight
		C	87.08
H	12.57
		S	0.23
N	0.12
		Metal content, μ g/g
Ca	0.4
		Fe	0.2
Na	0.6
		Ni	<0.1
V	<0.1
		Boiling range, DEG C
Initial boiling point	265
		10%	333
50%	426
		70%	470
95%	564

Table 3

As can be seen from the data of table 3, catalytic cracking catalyst of the present invention shows relatively high heavy oil utilization ratio, and gasoline selective is higher, coke selectivity good (coke selectivity is low); Gasoline and diesel oil total recovery higher, coke yield is lower.

Test case 2

This test case illustrates the hydrothermal structural stability of modified Y molecular sieve of the present invention.

By above-described embodiment 2,3,4 and the obtained phosphorus of comparative example 2,3,4 and rare earth modified Y zeolite sample 800 DEG C, carry out hydrothermal aging process in 2 hours, 4 hours, 8 hours, 17 hours, 24 hours respectively under 100% water vapor conditions, and it is carried out to the mensuration of degree of crystallinity, degree of crystallinity and crystallization reservation degree the results are shown in Fig. 1 and Fig. 2.

As can be seen from Fig. 1, Fig. 2, modified Y molecular sieve of the present invention is after hydrothermal aging process, and degree of crystallinity and crystallization reservation degree are significantly higher than comparative example.Illustrate that modified Y molecular sieve hydrothermal structural stability provided by the invention is better.

Test case 3

This example illustrates modified Y molecular sieve hydrothermal activity stability of the present invention and coke selectivity.

By above-described embodiment 2,5 and the obtained sample of comparative example 2,5 800 DEG C, carry out hydrothermal aging process in 2 hours, 4 hours, 8 hours, 17 hours, 24 hours respectively under 100% water vapor conditions, measure light oil microactivity (MA), and coke yield, calculate burnt turning and compare.The results are shown in Figure 3 and Fig. 4.

Embodiment 6

According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike, the Z3 molecular sieve of Z2 molecular sieve equivalent replaces, and is designated as C6.

Embodiment 7

According to the method Kaolinite Preparation of Catalyst of embodiment 1, unlike, replace Z2 molecular sieve with the Z3 molecular sieve of equivalent, be designated as C7.

Claims (12)

1. reduce coke yield and produce the catalytic cracking catalyst of gasoline, containing in the Modified Zeolite Y of butt 10 % by weight ~ 50 % by weight, to be no more than in butt 30 % by weight the specific Y zeolite containing rare earth, in the clay of butt 10 % by weight ~ 70 % by weight with the inorganic oxide binder of oxide basis 10 weight ~ 40 % by weight; Described Modified Zeolite Y: lattice constant is 2.420 ~ 2.440nm, by weight percentage, P is 0.05% ~ 6%, RE ₂o ₃be 0.03% ~ 10%, aluminum oxide is less than 22%, is less than 0.35mmol/g than hydroxyl nest concentration, described

In formula, M _{200 DEG C}, M _{500 DEG C}and M _{800 DEG C}represent respectively sample temperature 200 DEG C, 500 DEG C and 800 DEG C time the percent weight loss that records, C is sample crystallinity;

The described specific Y zeolite containing rare earth be rare earth modified gas phase super-stable Y molecular sieves and/or containing rare earth through acid-treated hydrothermal dealumination Y zeolite.

2. according to catalytic cracking catalyst described in claim 1, it is characterized in that, the lattice constant of described Modified Zeolite Y is 2.428nm ~ 2.438nm, and P content is 0.1% ~ 4.5%, RE by weight percentage ₂o ₃content is 0.1% ~ 4.5%, and alumina content is less than 21%, is less than 0.3mmol/g than hydroxyl nest concentration.

3. according to catalytic cracking catalyst according to claim 1, it is characterized in that, described catalyzer comprises the described specific Y zeolite containing rare earth of 0.5 % by weight ~ 30 % by weight.

4. the preparation method of the catalytic cracking catalyst described in any one of claims 1 to 3, the method comprises the Modified Zeolite Y described in preparation, by prepared Modified Zeolite Y, the described specific Y zeolite containing rare earth, clay and inorganic oxide binder mixing making beating and spray-dired step; Described Modified Zeolite Y take NaY molecular sieve as raw material, three exchange operations and three hydrothermal treatment consists are adopted to obtain with containing rare-earth substance and phosphorus containg substances, wherein, exchanged form is adopted containing rare-earth substance and phosphorus containg substances, add phosphorus containg substances exchange solution and exchange containing rare-earth substance exchange solution, phosphorus containg substances once or several times adds in arbitrary exchange operation, adds beyond a friendship containing rare-earth substance in arbitrary exchange operation.

5. according to the preparation method of catalytic cracking catalyst according to claim 4, it is characterized in that, described exchange operation comprises further and adds dealumination agent and carry out chemical dealuminization to promote removing of aluminium, and chemical dealuminization process is carried out in arbitrary exchange operation beyond handing over one.

6., according to the preparation method of catalytic cracking catalyst according to claim 4, it is characterized in that, described phosphorus containg substances be selected from ortho-phosphoric acid, phosphorous acid, tetra-sodium, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate and aluminum phosphate one or more.

7. according to the preparation method of catalytic cracking catalyst according to claim 4, it is characterized in that, described containing rare-earth substance be selected from lanthanum trioxide, cerium oxide, lanthanum nitrate, cerous nitrate, Lanthanum trichloride, Cerium II Chloride, nitric acid mishmetal and chlorination mishmetal one or more.

8. according to the preparation method of catalytic cracking catalyst according to claim 5, it is characterized in that, described dealumination agent be selected from ethylenediamine tetraacetic acid (EDTA), oxalic acid, citric acid, sulphosalicylic acid, silicofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, ammonium oxalate, Neutral ammonium fluoride, ammonium silicofluoride, ammonium borofluoride one or more.

9. according to the preparation method of the catalytic cracking catalyst described in any one of claim 4 ~ 8, it is characterized in that, the preparation method of described Modified Zeolite Y comprises the steps:

1) NaY molecular sieve and ammonium salt, phosphorus ammonium salt and water are according to NaY molecular sieve: ammonium salt: phosphorus ammonium salt: the part by weight of water=1:0.4 ~ 1.0:0 ~ 0.04:5 ~ 10 is mixed to get slurries, be 3.0 ~ 4.5 by the pH value of mineral acid adjusting slurry, then process at 70 DEG C ~ 95 DEG C and at least wash after 0.5h, wherein, NaY molecular sieve is in butt, and phosphorus ammonium salt is in elemental phosphorous; Described phosphorus ammonium salt is phosphorous ammonium salt;

2) by step 1) product that obtains under temperature 350 DEG C ~ 650 DEG C, 1% ~ 100% steam atmosphere roasting at least 0.5h obtain a roasting molecular sieve;

3) by step 2) obtain one roasting molecular sieve roast molecular sieve with phosphoric acid, dealumination agent according to one: phosphoric acid: dealumination agent: the part by weight of water=1:0 ~ 0.04:0.02 ~ 0.3:5 ~ 10 mixes, with mineral acid adjust pH 2.4 ~ 3.5, then at 50 DEG C ~ 90 DEG C, at least 0.5 hour is processed, filter, wash, washing water temperature >=50 DEG C, wherein, a roasting molecular sieve is in butt, and phosphoric acid is in elemental phosphorous;

4) by step 3) product that obtains temperature 350 DEG C ~ 650 DEG C, under 1% ~ 100% steam atmosphere roasting at least 0.5h obtain two roasting molecular sieves;

5) by step 4) obtain two roasting molecular sieves roast molecular sieve with rare earth chloride and water according to two: rare earth chloride: the part by weight of water=1:0.01 ~ 0.05:5 ~ 10 mixes, then processes at least 0.5 hour at 70 DEG C ~ 90 DEG C, filtration; Washing, washing water temperature>=50 DEG C, wherein, two roasting molecular sieves are in butt, and rare earth chloride is with RE ₂o ₃meter;

6) by step 5) product that obtains 350 DEG C ~ 650 DEG C, under 1% ~ 100% steam atmosphere roasting at least 0.5h obtain Modified Zeolite Y.

10. according to the preparation method of catalytic cracking catalyst according to claim 9, it is characterized in that, described binding agent is selected from one or more in gama-alumina, η-aluminum oxide, θ-aluminum oxide, χ-aluminum oxide, pseudo-boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite); Described clay is selected from one or more in kaolin, polynite, diatomite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.

11. according to the preparation method of catalytic cracking catalyst according to claim 10, and it is characterized in that, described kaolin is halloysite.

12. according to the preparation method of catalytic cracking catalyst according to claim 4, it is characterized in that, described binding agent is selected from one or more in gama-alumina, η-aluminum oxide, θ-aluminum oxide, χ-aluminum oxide, pseudo-boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite); Described clay is selected from one or more in kaolin, polynite, diatomite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite.