CN103506153A - Catalytic cracking catalyst for reducing coke yield and producing gasoline - Google Patents
Catalytic cracking catalyst for reducing coke yield and producing gasoline Download PDFInfo
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- CN103506153A CN103506153A CN201210217714.9A CN201210217714A CN103506153A CN 103506153 A CN103506153 A CN 103506153A CN 201210217714 A CN201210217714 A CN 201210217714A CN 103506153 A CN103506153 A CN 103506153A
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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
Technical field
The present invention relates to a kind of hydrocarbon oil catalytic cracking catalyst, further relate to a kind of catalytic cracking catalyst that reduces coke yield and improve gasoline selective.
Background technology
Along with the minimizing day by day of petroleum resources, petroleum heaviness, in poor quality have become undisputable fact.As being the main manufacturing process of gasoline and diesel oil light-weight fuel oil by heavy oil transformation, catalytic cracking inevitably needs to process more heavy oil feedstocks more inferior.The reduction of conversion ratio and the increase of coke yield are that feedstock oil heaviness in poor quality is brought one of performance of impact to catalytic cracking.Be directed to this, people from molecular sieve modified, catalyst be fabricated onto technological design aspect carried out a large amount of research (Liu Tao, Zhang Zhongdong, Haitao Zhang etc. energy .2009, the 14(1 of China and foreign countries): 71-77).Yet the Catalyst Design of most and commercial plant operation are all to realize the high yield of light oil and liquefied gas product by improving cracking reaction conversion ratio, cause coke yield obviously higher, have caused the waste of feedstock oil resource.Improve heavy oil utilization rate, can suitably control conversion ratio, reduce coke yield, to improve coke selectivity.In the composition of FCC catalyst, molecular sieve has conclusive impact to the combined reaction performance of catalyst, and therefore molecular sieve being carried out to modification is to improve one of the most effective means of catalytic cracking catalyst reactivity worth.
Coke is comprised of the different poor hydrogen compound of various scarce hydrogen degree, is the product of hydrogen transfer reaction, thereby will reduces coke yield, needs suitably to reduce hydrogen transfer reaction.The main process of hydrogen transfer reaction is that protonated alkene is at absorption, reaction and the desorption at acidic zeolite center.Molecular sieve acid site density is high, and hydrogen transfer reaction 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 reaction 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 reaction is relatively few, and coke yield reduces.To guarantee the coke selectivity that active component has had as can be seen here, must make active component there is low lattice constant, appropriate sour density.
As everyone knows, cracking unit, in operation process, for maintaining the stable of reactivity, need to constantly draw off old dose, fresh makeup catalyst.Thereby there is age distribution in catalyst.Its reactivity worth of the catalyst of all ages and classes is different.In fresh catalyst, molecular sieve structure cell is larger, and cracking activity is high, and hydrogen migration ability is strong, and coke yield is high; And catalyst molecular sieve generation framework dealumination under hydrothermal condition of long-term running, structural breakdown, declines catalyst cracking activity, reaction selectivity variation.Obviously the catalyst of this two states is all unfavorable for the raising of heavy oil utilization rate.Improve catalyst heavy oil utilization rate, will start with from improving the reactivity worth of molecular sieve under different level of deactivation, use on the one hand the molecular sieve of low unit cell dimension, to reduce the coke selectivity of fresh molecular sieve, on the other hand, by modification, improve molecular sieve activity stability, to improve equilibrium activity, dwindle as far as possible the active difference of zeolite-water heat ageing when different phase, to reduce on the whole the coke selectivity of catalyst, thereby improve heavy oil utilization rate.
Use the Y zeolite of low unit cell dimension must make catalyst activity and heavy oil conversion performance decline, must add other modifying element to improve the performance of active component 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, the method for modifying of molecular sieve is introduced phosphorus and rare earth in people's employing jointly, further to improve catalytic performance.
CN1624079A discloses a kind of hydrocarbon cracking catalyzer containing modcfied faujasite, first the method for modifying of its mesolite for carrying out exchange reaction by faujasite and phosphorus compound and ammonium compounds, water and zeolite weight ratio 2～25, pH2.0～6.5, temperature is 10～150 ℃, be 0.1～4 hour swap time, then in exchange slurries, introduce earth solution, reaction time is 1～60 minute, further reaction, after filtration, washing, through phosphorus and rare earth modified zeolite at 250～800 ℃, roasting 0.1～3.5 hour under 1～100% steam and obtaining.Adopt the lattice constant 2.440～2.465nm of modified zeolite prepared by this method of modifying, sodium oxide molybdena 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, and heavy oil cracking ability and preventing from heavy metal pollution ability are strong.The catalyst that adopts this modified molecular screen to prepare has higher yield of gasoline and good coke selectivity.But the molecular sieve lattice constant obtaining by this preparation method is larger, will affect molecular sieve catalyst coke selectivity.
CN 1506161A discloses a kind of hyperastable Y-type RE molecular sieve active component, 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 molybdena 0.3～2.5, degree of crystallinity 30～55%, lattice constant 2.455～2.472 nanometers.Molecular sieve be take NaY zeolite as raw material, through rare earth exchanged and roasting for the first time, obtains " one hands over a roasting " rare earth NaY; React with rare earth, phosphorus containg substances and ammonium salt again, carry out calcination process for the second time, obtain with phosphorus and rare earth modified modified Y zeolite.This modified molecular screen coke yield is moderate.The molecular sieve content of rare earth making is by this method higher, and lattice constant is large, and molecular sieve coke selectivity is affected.
CN1317547A discloses a kind of FCC catalyst, wherein contain the composite modified Y zeolite of a kind of phosphorus and rare earth, this molecular sieve by NaY zeolite through rare earth and ammonium salt hybrid switching again after hydrothermal calcine is processed, react with phosphorus compound, then carry out calcination process preparation for the second time, wherein RE
2o
3the weight ratio of/Y zeolite is 0.02～0.18, and the weight ratio of ammonium salt/Y zeolite is that the weight ratio of 0.1～1.0, P/Y zeolite is 0.003～0.05,250～750 ℃ of sintering temperatures, water vapor condition 5～100%, 0.2～3.5 hour time.
CN 101537366A has reported a kind of modified molecular screen that improves coking behavior, it is characterized in that the preparation method through two friendship two roastings obtains this molecular sieve by NaY molecular sieve, by weight percentage, and RE
2o
3be 0.05～4.0%, P is 0.05～5.0%, structure cell is that 2.430～2.440nm, degree of crystallinity are 35～55%.This molecular sieve have more to middle macropore pore volume and good stability, when reducing catalyst coke productive rate, heavy oil pyrolysis ability further improves, thereby total liquid is received, improves, and is particularly conducive to the raising of yield of light oil.
EP 0421422 has mentioned a kind of faujasite for hydrocracking catalyst, it is characterized in that this faujasite is at wave number 3740 ± 10cm
-1has 20% INFRARED ABSORPTION at least, at wave number 3560 ± 10cm
-1have 5% INFRARED ABSORPTION at least, the former is at least 2 than the latter.This faujasite specific area is 650m at least
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 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 the more than 45% of total pore volume, and non-framework aluminum accounts for the more than 30% of whole alumiunum amount, infrared acidity 0.15～0.55mmol/g.This modified zeolite be take NaY as raw material, through processes such as ammonium exchange, hydrothermal treatment consists, de-non-framework aluminum, reaming, intermediate water heat treatments, makes.Zeolite after modification can be used as the acidic components of various catalyst, as middle oil type hydrocracking catalyst.
Above several pieces of patent documentations by hydrothermal dealumination and (or) method of chemical dealuminization improves the silica alumina ratio of Y zeolite, 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) in process, tend to cause zeolite structured destruction, zeolite crystallinity is declined.
US 5013699 has proposed a kind of processing method of Y zeolite, be by NaY zeolite through ammonium ion exchange, then carry out high-temperature vapor processing, sample carries out ammonium exchange again and removes aluminium under the condition of PH < 4, obtains zeolite product.This processing method adopts and process zeolite sample under low ph condition, and does not adopt safeguard measure, easily causes zeolitic frameworks to destroy, and zeolite crystallinity is reduced.
US 4503023 discloses a kind of LZ～210 zeolite and preparation method thereof, NaY zeolite is carried out to the silica alumina ratio that dealumination complement silicon improves zeolite with fluosilicate, the product degree of crystallinity obtaining is higher, but while adopting fluosilicate to carry out dealuminzation to Y zeolite, the SiO of zeolite product
2/ Al
2o
3mol ratio conventionally can not be higher than 13, otherwise the degree of crystallinity of zeolite product will significantly decline.In addition, modified Y zeolite secondary pore prepared by the method that adopts fluosilicate to carry out dealumination complement silicon is few, for being used as heavy oil catalytic cracking reaction, is disadvantageous.
Summary of the invention
The catalytic cracking catalyst that the object of this invention is to provide a kind of voluminous gasoline, contains the phosphorus of a kind of " three hand over three roastings " and rare earth modified Y zeolite in this catalyst, can improve gasoline selective, reduces coke yield.
The invention provides a kind of catalytic cracking catalyst that reduces coke yield high-yield diesel oil, contain Modified Zeolite Y in butt 10 % by weight ~ 50 % by weight, in butt be no more than the specific Y zeolite containing rare earth of 30 % by weight, in the clay of butt 10 % by weight ~ 70 % by weight with in the inorganic oxide binder of oxide 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%, aluminium oxide is less than 22%, than hydroxyl nest concentration, is less than 0.35mmol/g, described
In formula, M
200 ℃, M
500 ℃and M
800 ℃represent respectively the percent weight loss that sample records when 200 ℃ of temperature, 500 ℃ and 800 ℃, C is sample degree of 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 that preparation is described, and prepared Modified Zeolite Y, the described specific Y zeolite containing rare earth, clay and inorganic oxide binder are mixed to making beating, spray-dired step;
Described Modified Zeolite Y (also claiming to be phosphorous and Modified Zeolite Y rare earth) can (be to obtain through the preparation method of three friendships three roastings, it is so-called that " three hand over the general abbreviation of San Bei”Shi this area to a kind of molecular sieve modified technique, finger be take NaY molecular sieve as 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 also can add dealumination agent to promote removing of aluminium, chemical dealuminization process can be carried out in arbitrary exchange operation beyond a friendship.After exchange, filtering, washing is conventional method.
Described catalytic cracking catalyst of the present invention can show good stability in catalytic cracking process, for RFCC, can reduce green coke, improves gasoline selective, improves heavy oil utilization rate.
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.
The specific embodiment
Modified Zeolite Y of the present invention is phosphorous and Modified Zeolite Y rare earth, that the preparation method through " three hand over three roastings " obtains by NaY molecular sieve, 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%, be preferably 0.1～4.5%, RE
2o
3be 0.03～10%, be preferably 0.1～4.5%, aluminium oxide is less than 22%, is generally 10-22%, is preferably and is less than 20%, than hydroxyl nest concentration, is less than 0.35mmol/g, for example, be 0.01mmol/ ~ 0.35mmol/g, is preferably less than 0.3mmol/g, described
In formula, M
200 ℃, M
500 ℃and M
800 ℃represent respectively the percent weight loss that sample records when 200 ℃ of temperature, 500 ℃ and 800 ℃, C is sample degree of crystallinity.
Zeolite molecular sieve framework dealumination ，Qi Lv room forms " the hydroxyl nest " consisting of four adjacent Si-OH, is the rejected region in zeolite molecular sieve lattice, and its quantity and zeolite structured stability have direct relation." hydroxyl nest " quantity is more, illustrates that the aluminium room forming because of framework dealumination on molecular sieve is more, and the structural stability of molecular sieve is poorer.The aluminium room that Y zeolite forms in hydro-thermal or chemical dealuminization process is filled by the silicon dissociating, in the modifying process of molecular sieve, dealumination process and treatment conditions directly have influence on the stability of modified molecular screen, inventor 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 forms can fully be filled by silicon, hydroxyl nest quantity reduces, so 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): the method 1094～1097) providing characterizes.This characterizing method is sample to be carried out to thermogravimetric analysis calculate.
On weight-loss curve, 200 ℃ of following weightlessness corresponding to desorption attached water, 200 ℃～500 ℃ weightlessness corresponding to the de-ammonium of zeolite and the dehydration of hydroxyl nest, 500 ℃～800 ℃ weightlessness corresponding to dehydroxylation.NH4 on Y zeolite
+decompose and just produce acid hydroxy group, so the molal quantity of hydroxyl is corresponding with NH3.By 500 ℃～800 ℃ weight-loss curves, calculated after hydroxyl molal quantity like this, be converted into NH
3quality, then the weight loss of calculating from 200 ℃～500 ℃ weight-loss curves deducts NH3 amount, just can calculate the molal quantity of hydroxyl nest.
In the calculating of hydroxyl nest concentration, a hydroxyl nest, because de-two molecular waters disappear, takes off a part water therefore its mole is 36, two hydroxyls, therefore its mole is 9.
The preparation method of above-mentioned Modified Zeolite Y, to take NaY molecular sieve as raw material, preparation process through " three hand over three roastings " obtains, it is so-called that " three hand over the general abbreviation of San Bei”Shi this area to a kind of molecular sieve modified technique, 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 also can add dealumination agent to 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 is selected from one or more in orthophosphoric acid, phosphorous acid, pyrophosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), aluminum phosphate.
In described ammonium salt solution, containing ammonium material, be selected from one or more in ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium sulfate, ammonium hydrogen sulfate.
Described containing being selected from one or more in lanthana, cerium oxide, lanthanum nitrate, cerous nitrate, lanthanum chloride, cerium chloride, nitric acid mishmetal, chlorination mishmetal containing rare-earth substance in rare earth exchanged liquid.
The inorganic acid of described adjusting exchange liquid pH value is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid.
Described dealumination agent is selected from organic acid (comprising ethylenediamine tetra-acetic acid, oxalic acid, citric acid, sulfosalicylic acid), inorganic acid (comprising fluosilicic acid, hydrochloric acid, sulfuric acid, nitric acid), organic and inorganic salts (comprising ammonium oxalate, ammonium fluoride, ammonium fluosilicate, ammonium fluoroborate).
A kind of preparation process of preferred Modified Zeolite Y can be to 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, by the pH value of inorganic acid adjusting slurry, be 3.0～4.5, then at 70 ℃～95 ℃, process at least 0.5h, washing after common 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, for example one or more in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium pyrophosphate, ammonium phosphite;
2) product step 1) being obtained is roasting 0.5h at least under 350 ℃～650 ℃ of temperature, 1%～100% steam atmosphere, common 0.5 ~ 10 hour, preferably within 2 ~ 6 hours, obtains a roasting molecular sieve;
3) by step 2) roasting molecular sieve and the phosphoric acid that obtains, dealumination agent is according to a roasting molecular sieve: phosphoric acid: dealumination agent: the part by weight of water=1:0～0.04:0.02～0.3:5～10 mixes, with inorganic acid adjust pH 2.4～3.5, then at 50 ℃～90 ℃, process at least 0.5 hour, common 0.5 ~ 10 hour, filter, wash, washing water temperature >=50 ℃, be generally 50 ~ 95 ℃, wherein, a roasting molecular sieve is in butt, and phosphoric acid is in elemental phosphorous.
4) product step 3) being obtained is 350 ℃～650 ℃ of temperature, and under 1%～100% steam atmosphere, roasting 0.5h at least, common 0.5 ~ 10 hour, preferably obtains two roasting molecular sieves for 2 ~ 6 hours;
5) two roasting molecular sieves and the rare earth chlorides that step 4) obtained and water are according to two roasting molecular sieves: rare earth chloride: the part by weight of water=1:0.01～0.05:5～10 mixes, then at 70 ℃～90 ℃, process at least 0.5 hour, common 0.5 ~ 10 hour, filter; Washing, washing water temperature>=50 ℃, are generally 50 ~ 95 ℃, and wherein, two roasting molecular sieves are in butt, and rare earth chloride is with RE
2o
3meter;
6) product step 5) being obtained is roasting 0.5h at least under 350 ℃～650 ℃, 1%～100% steam atmosphere, common 0.5 ~ 10 hour, preferably within 2 ~ 6 hours, obtains Modified Zeolite Y.
According to catalyst 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 catalyst 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 the 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 ℃, 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 the second Y zeolite can be with reference to patent CN1286721C, particularly embodiment 5,6 and 8 wherein; Preferably the content of described the 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: the acid solution that is 0.01-2N by super-stable Y molecular sieves and concentration fully mixes at 20-100 ℃ with the ratio of liquid-solid ratio (weight) 4-20, process washing after 10-300 minute, filter, add again rare earths salt to carry out rare earth ion exchanged, after exchange, wash successively, filter and be dried.The concrete preparation method of described the 3rd Y zeolite can be with reference to patent CN100497175C, particularly embodiment 1-6 wherein.
Preferably, the described specific Y zeolite containing rare earth is described the 3rd Y zeolite, and its content is preferably 10 ~ 30 % by weight.
In catalyst prepared by the present invention, also can contain except described Modified Zeolite Y and described specific containing other molecular sieve the Y zeolite of rare earth one or more of conventional other Y zeolite in described other molecular screening catalytic cracking catalyst, the molecular sieve with MFI structure, Beta molecular sieve, non-zeolite molecular sieve.Other described Y zeolite is one or more in REY molecular sieve, USY molecular sieve, HY molecular sieve, DASY molecular sieve, REHY molecular sieve for example; The described molecular sieve with MFI structure is one or more in ZSM-5, ZRP, ZSP molecular sieve for example; Described non-zeolite molecular sieve is one or more in SAPO, HTS for example.The content of described other molecular sieve is preferably no more than 10 % by weight.
Catalytic cracking catalyst provided by the invention, contain described Modified Zeolite Y in butt 10 % by weight-50 % by weight, in butt be no more than the specific Y zeolite containing rare earth of 30 % by weight, in the clay of butt 10 % by weight-70 % by weight with in the inorganic oxide binder of oxide 10 % by weight-40 % by weight.The content of the described specific Y zeolite containing rare earth is preferably 0.5-30 % by weight, more preferably 2 ~ 25 % by weight.Preferably, in described catalytic cracking catalyst, contain the described Modified Zeolite Y of 15 ~ 35 % by weight, in the DASY molecular sieve of butt 2 ~ 10 % by weight.
According to catalyst of the present invention, wherein said clay is selected from as one or more in the clay of Cracking catalyst component, for example one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.These clays are that those of ordinary skills are known.
Binding agent of the present invention is one or more in the inorganic oxide binder that catalytic cracking catalyst is conventional, preferential oxidation al binder, described alumina binder is selected from one or more in aluminium oxide, hydrated alumina and the aluminium colloidal sol of common the used various forms of Cracking catalyst.For example, be selected from one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite), preferably the double aluminium binder of boehmite and aluminium colloidal sol.
Catalyst of the present invention can be according to preparation method's preparation of any existing Cracking catalyst, for example clay, molecular sieve, alumina binder are mixed to making beating, dry and the washing of spraying, filtration, dry step, these methods have detailed description in patent CN1098130A, CN1362472A, CN1727442A, CN1132898C, CN1727445A, quote as a reference in the lump here.
Spraying is dried, washs, is dried as prior art, and the present invention does not have specific (special) requirements.
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
Ammonium dihydrogen phosphate (ADP), chemical pure
Sulfuric acid, chemical pure
Oxalic acid, solid, chemical pure
Fluosilicic acid, technical grade
Hydrochloric acid, chemical pure
The second Y zeolite (Z2) containing rare earth makes according to the method for embodiment 5 in patent CN1286721C;
The 3rd Y zeolite (Z3) containing rare earth makes according to the method for patent CN100497175C embodiment 1;
DASY-2.0 molecular sieve is catalyst asphalt in Shenli Refinery of China Petrochemical Industry commercially available prod
Aluminium colloidal sol is the commercial goods of catalyst 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;
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 Deng， Science Press, nineteen ninety version) measure.
In the concentration determination of hydroxyl nest, the thermogravimetric analysis data acquisition of sample is measured by hereinbefore described thermogravimetric method.
Catalytic cracking catalyst micro-activity (MA) is measured with reference to RIPP 92-90 standard method.
Usage ratio described in embodiment and comparative example does not have the weight ratio that is of specified otherwise.
Described sour aluminum ratio is the hydrochloric acid of concentration 36 % by weight and weight ratio in the boehmite of aluminium oxide.
Embodiment 1
(1) preparation of modified molecular screen
The NaY molecular sieve of take exchanges with ammonium sulfate as raw material, and treatment conditions are: NaY molecular sieve (butt): ammonium sulfate: water=1:1.0:8(weight ratio), and 3.5,85 ℃ of exchange 1h of sulfuric acid adjust pH, washing.Hydrothermal calcine is processed, 580 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated one roasting containing rare earth, treatment conditions are: a roasting molecular sieve (butt): rare earth chloride (is pressed RE
2o
3meter): water=1:0.042:8(weight ratio), 70 ℃ of exchange 1h, deionized water washing.Hydrothermal calcine is processed, 580 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated two roastings of phosphoric acid and oxalic acid, treatment conditions are: two roasting molecular sieves (butt): phosphoric acid (by P): oxalic acid (containing two molecular crystalline water): water=1:0.014:0.14:8(weight ratio), with 2.8,70 ℃ of sulfuric acid adjust pHs, process 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, and 70% steam roasting time 2h, obtains modified molecular screen, is designated as A1, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
The boehmite of 20 weight portions in aluminium oxide is mixed to making beating with deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, (described sour aluminum ratio is the hydrochloric acid of concentration 36 % by weight and weight ratio in the boehmite of aluminium oxide to acid aluminum ratio, lower same) be 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively kaolinic slurries of 30 weight portion in butt (solid content 45 % by weight, lower with), in the aluminium colloidal sol (Al of 10 weight portions of aluminium oxide
2o
3content is 21.5 % by weight), stir 20 minutes, add wherein more afterwards described A1 molecular sieve in 35 weight portions of butt, in the Z2 molecular sieve (the second Y zeolite containing rare earth) of butt 5 weight portions, continue to stir 30 minutes, obtaining solid content is 30 % by weight slurries, the dry microspherical catalyst of making of spraying.By the roasting 1 hour at 500 ℃ of this microspherical catalyst, then at 60 ℃ with (NH
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, after filtration, at 120 ℃, dries, and obtains catalytic cracking catalyst C1.
Comparative example 1
(1) preparation of modified molecular screen
Method according to patent CN 101537366A is prepared modified Y molecular sieve.
Get 100 grams of (butt) NaY molecular sieves, pour into 1000g exchange solution ((NH4) containing 0.63% is housed
2hPO
4salt and 8.58% NH
4cl) in reactor, at 90 ℃ of exchange 1h, in exchange process, control pH value of solution=3.0～3.5 simultaneously, after exchange, filter washing; Under 730 ℃, 100% steam exist, after roasting 2h, calcining matter is poured into the 1200g exchange solution (RECl containing 0.58% is housed
3with 6.8% NH
4cl salt) in reactor, at 90 ℃ of exchange 1h, and in exchange process, control pH value of solution=6.0～6.5, after exchange, filter, washing, roasting 2h under 730 ℃, 70% steam exist, makes modified molecular screen, is designated as B1, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
According to the method for step (2) in embodiment 1, prepare catalytic cracking catalyst, difference is with described modified molecular screen B1, to replace described modified molecular screen A1, thereby make catalytic cracking catalyst DC1.
Embodiment 2
(1) preparation of modified molecular screen
The NaY molecular sieve of take exchanges with ammonium chloride solution as raw material, and treatment conditions are: NaY molecular sieve (butt): ammonium chloride: water=1:0.8:8,4.0,90 ℃ of exchange 1h of hydrochloric acid adjust pH, washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, 80% steam roasting time 2h.With phosphoric acid and silicate fluoride solution, process the rear sample of a roasting, treatment conditions are: a roasting molecular sieve (butt): phosphoric acid (by P): fluosilicic acid: water=1:0.01:0.03:8, and hydrochloric acid is adjusted pH2.8, and 70 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, 70% steam roasting time 2h.With sample after solution-treated two roastings containing rare earth, treatment conditions are: two roasting molecular sieves (butt): rare earth chloride (is pressed RE
2o
3meter): water=1:0.03:8,70 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, and 100% steam roasting time 2h, obtains modified molecular screen, is designated as A2, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
The boehmite of 20 weight portions in aluminium oxide is mixed to making beating with deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, acid aluminum ratio is 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively kaolinic slurries of 30 weight portion in butt (solid content 45 % by weight, lower with), in the aluminium colloidal sol (Al of 10 weight portions of aluminium oxide
2o
3content is 21.5 % by weight), stir 20 minutes, add wherein more afterwards described A2 molecular sieve, the Z2 molecular sieve of 13 weight portions and the Z3 molecular sieve of 2 weight portions in 25 weight portions of butt, the dry microspherical catalyst of making of spraying after continuing to stir.By the roasting 1 hour at 500 ℃ of this microspherical catalyst, then at 60 ℃ with (NH
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, after filtration, at 120 ℃, dries, and obtains catalytic cracking catalyst C2.
Comparative example 2
(1) preparation of modified molecular screen
Method according to patent CN 101537366A is prepared modified Y molecular sieve.
Get 100 grams of (butt) NaY molecular sieves, pour into and 900g exchange solution is housed (containing (NH of 0.45 % by weight
4)
2hPO
4(the NH of salt and 10 % by weight
4)
2sO
4) reactor in, at 90 ℃ of exchange 1h, in exchange process, control pH value of solution=3.0～3.5 simultaneously, after exchange, filter washing; Under 730 ℃, 100% steam exist, after roasting 2h, calcining matter is poured into and 1200g exchange solution is housed (containing the RECl of 0.44 % by weight
3nH with 7.8 % by weight
4cl salt) in reactor, at 90 ℃ of exchange 1h, and in exchange process, control pH value of solution=6.0～6.5, after exchange, filter, washing, roasting 2h under 730 ℃, 100% steam exist, makes modified molecular screen, is designated as B2, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
According to the method for step (2) in embodiment 2, prepare catalytic cracking catalyst, difference is with described modified molecular screen B2, to replace described modified molecular screen A2, thereby make catalytic cracking catalyst DC2.
Embodiment 3
(1) preparation of modified molecular screen
The NaY molecular sieve of take exchanges with ammonium sulfate as raw material, and treatment conditions are: NaY molecular sieve (butt): ammonium sulfate: water=1:1.0:10,3.5,90 ℃ of exchange 2h of sulfuric acid adjust pH, washing.Hydrothermal calcine is processed, 580 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated one roasting of phosphate-containing and oxalic acid, treatment conditions are: a roasting molecular sieve (butt): diammonium hydrogen phosphate (by P): oxalic acid: water=1:0.018:0.03:8, and hydrochloric acid is adjusted pH=3.0, and 70 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated two roastings containing rare earth, treatment conditions are: two roasting molecular sieves (butt): rare earth chloride (is pressed RE
2o
3meter): water=1:0.02:8.0,85 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 580 ℃ of sintering temperatures, and 100% water steams roasting time 2h, obtains modified molecular screen, is designated as A3, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
The boehmite of 20 weight portions in aluminium oxide is mixed to making beating with a certain amount of deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, acid aluminum ratio is 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively kaolinic slurries of 30 weight portion in butt, in the aluminium colloidal sol (Al of 10 weight portions of aluminium oxide
2o
3content is 21.5 % by weight), stir 20 minutes, add wherein more afterwards in the described A3 molecular sieve of 15 weight portions of butt, the Z3 molecular sieve of 25 weight portions the dry microspherical catalyst of making of spraying after continuing to stir.By the roasting 1 hour at 500 ℃ of this microspherical catalyst, then at 60 ℃ with (NH
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, after filtration, at 120 ℃, dries, and obtains catalytic cracking catalyst C3.
Comparative example 3
(1) preparation of modified molecular screen
Method according to patent CN 101537366A is prepared modified Y molecular sieve.
Get 100 grams of (butt) NaY molecular sieves, pour into 1000g exchange the solution ((NH containing 0.63% is housed
4)
2hPO
4salt and 10% (NH
4)
2sO
4) reactor in, at 90 ℃ of exchange 1h, in exchange process, control pH value of solution=3.0～3.5 simultaneously, after exchange, filter washing; Under 670 ℃, 100% steam exist, after roasting 2h, calcining matter is poured into the 400g exchange solution (RECl containing 0.60% is housed
3with 6.8% NH
4cl salt) in reactor, at 90 ℃ of exchange 1h, and in exchange process, control pH value of solution=6.0～6.5, after exchange, filter, washing, roasting 2h under 700 ℃, 100% steam exist, makes modified molecular screen, is designated as B3, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
According to the method for step (2) in embodiment 3, prepare catalytic cracking catalyst, difference is with described modified molecular screen B3, to replace described modified molecular screen A3, thereby make catalytic cracking catalyst DC3.
Embodiment 4
(1) preparation of modified molecular screen
The NaY molecular sieve of take exchanges with ammonium phosphate and ammonium sulfate as raw material, and treatment conditions are: NaY molecular sieve (butt): ammonium dihydrogen phosphate (ADP) (by P): ammonium sulfate: water=1:0.05:1.0:8,3.0,85 ℃ of exchange 1h of sulfuric acid adjust pH, washing.Hydrothermal calcine is processed, 580 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated one roasting containing oxalic acid, treatment conditions are: a roasting molecular sieve (butt): oxalic acid: water=1:0.15:0.020:8, and 70 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated two roastings containing rare earth, treatment conditions are: two roasting molecular sieves (butt): rare earth chloride (is pressed RE
2o
3meter): water=1:0.01:8,70 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 600 ℃ of sintering temperatures, and 100% steam roasting time 2h, obtains modified molecular screen, is designated as A4, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
The boehmite of 20 weight portions in aluminium oxide is mixed to making beating with a certain amount of deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, acid aluminum ratio is 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively kaolinic slurries of 28 weight portion in butt, in the aluminium colloidal sol (Al of 10 weight portions of aluminium oxide
2o
3content is 21.5 % by weight), stir 20 minutes, add wherein more afterwards described modified molecular screen A4,2 weight portion Z2 molecular sieves in 40 weight portions of butt, the dry microspherical catalyst of making of spraying after continuing to stir.By the roasting 1 hour at 500 ℃ of this microspherical catalyst, then at 60 ℃ with (NH
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, after filtration, at 120 ℃, dries, and obtains catalytic cracking catalyst C4.
Comparative example 4
(1) preparation of modified molecular screen
Method according to patent CN 101537366A is prepared modified Y molecular sieve.
Get 100 grams of (butt) NaY molecular sieves, pour into 1200g exchange the solution ((NH containing 1.22% is housed
4)
2hPO
4salt and 8.58% NH
4cl) in reactor, at 90 ℃ of exchange 1h, in exchange process, control pH value of solution=5.0-5.5 simultaneously, after exchange, filter washing; Under 620 ℃, 100% steam exist, after roasting 2h, calcining matter is poured into the 1200g exchange solution (RECl containing 0.055% is housed
3with 7.8% NH
4cl salt) in reactor, at 90 ℃ of exchange 1h, and in exchange process, control pH value of solution=6.0～6.5, after exchange, filter, washing, roasting 2h under 700 ℃, 100% steam exist, makes modified molecular screen, is designated as B4, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
According to the method for step (2) in embodiment 4, prepare catalytic cracking catalyst, difference is with described modified molecular screen B4, to replace described modified molecular screen A4, thereby make catalytic cracking catalyst DC4.
(1) preparation of modified molecular screen
The NaY molecular sieve of take exchanges as raw material ammonium phosphate and ammonium sulfate, and treatment conditions are: NaY molecular sieve (butt): ammonium dihydrogen phosphate (ADP) (by P): ammonium sulfate: water=1:0.05:1.0:8, and, 3.5,90 ℃ of exchange 2h of sulfuric acid adjust pH, washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated one roasting containing rare earth, treatment conditions are: a roasting molecular sieve (butt): rare earth chloride (is pressed RE
2o
3meter): water=1:0.02:8.0, hydrochloric acid is adjusted pH2.9, and 85 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 580 ℃ of sintering temperatures, 100% steam roasting time 2h.With sample after solution-treated two roastings of phosphate-containing and fluosilicic acid, treatment conditions are: two roasting molecular sieves (butt): diammonium hydrogen phosphate (by P): fluosilicic acid: water=1:0.006:0.03:8, and hydrochloric acid is adjusted pH=3.0, and 70 ℃ of exchange 1h, filter; Deionized water washing.Hydrothermal calcine is processed, 550 ℃ of sintering temperatures, and 100% water steams roasting time 2h, obtains modified molecular screen, is designated as A5, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
The boehmite of 20 weight portions in aluminium oxide is mixed to making beating with a certain amount of deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, acid aluminum ratio is 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively kaolinic slurries of 30 weight portion in butt, in the aluminium colloidal sol (Al of 10 weight portions of aluminium oxide
2o
3content is 21.5 % by weight), stir 20 minutes, add wherein more afterwards described modified molecular screen A5, the Z3 molecular sieve of 30 weight portions and the DASY-2.0 molecular sieve of 5 weight portions in 5 weight portions of butt, the dry microspherical catalyst of making of spraying after continuing to stir.By the roasting 1 hour at 500 ℃ of this microspherical catalyst, then at 60 ℃ with (NH
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, after filtration, at 120 ℃, dries, and obtains catalytic cracking catalyst C5.
Comparative example 5
(1) preparation of modified molecular screen
Method according to patent CN 101537366A is prepared modified Y molecular sieve.
Get 100 grams of (butt) NaY molecular sieves, pour into 1500g exchange the solution ((NH containing 1.11% is housed
4)
2hPO
4salt and 8.58% NH
4cl) in reactor, at 90 ℃ of exchange 1h, in exchange process, control pH value of solution=4.5-5.0 simultaneously, after exchange, filter washing; Under 650 ℃, 100% steam exist, after roasting 2h, calcining matter is poured into the 1000g exchange solution (RECl containing 0.35% is housed
3with 7.8% NH
4cl salt) in reactor, at 90 ℃ of exchange 1h, and in exchange process, control pH value of solution=6.0～6.5, after exchange, filter, washing, roasting 2h under 700 ℃, 70% steam exist, makes modified molecular screen, is designated as B5, and physico-chemical property characterization result is listed in table 1.
(2) preparation of catalytic cracking catalyst
According to the method for step (2) in embodiment 5, prepare catalytic cracking catalyst, difference is with described modified molecular screen B5, to replace described modified molecular screen A5, thereby make catalytic cracking catalyst DC5.
Comparative example 6
Method according to embodiment 1 is prepared catalytic cracking catalyst, with the Z3 molecular sieve of equivalent, replaces the A1 molecular sieve in embodiment 1, is designated as DC6.
Table 1
Test case 1
The explanation of this test case adopts the cracking reaction performance of catalytic cracking catalyst of the present invention.
By above-mentioned catalytic cracking catalyst C1-C5 and DC1-DC6, under 800 ℃, 100% water vapour condition aging 8 hours, the reactivity worth of catalyst is evaluated by small fixed flowing bed ACE R+ device (being manufactured and designed by U.S. Kayser Technology Inc. company), catalyst filling amount 9g.At 518 ℃ of reaction temperatures, air speed 16h
-1, under oil ratio (weight) condition that is 5.5, using the catalytic mixing oil shown in table 2 as feedstock 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, ℃ | 34 |
| Carbon residue, % by weight | 0.25 |
| Constituent content, % by weight | |
| C | 87.08 |
| H | 12.57 |
| S | 0.23 |
| N | 0.12 |
| Tenor, μ g/g | |
| Ca | 0.4 |
| Fe | 0.2 |
| Na | 0.6 |
| Ni | <0.1 |
| V | <0.1 |
| Boiling range, ℃ | |
| Initial boiling point | 265 |
| 10% | 333 |
| 50% | 426 |
| 70% | 470 |
| 95% | 564 |
Table 3
Data by table 3 can find out, catalytic cracking catalyst of the present invention shows relatively high heavy oil utilization rate, and gasoline selective is higher, coke selectivity good (coke selectivity is low); Gasoline and diesel oil total recovery are higher, and coke yield is lower.
Test case 2
This test case illustrates the hydro-thermal structural stability of modified Y molecular sieve of the present invention.
The phosphorus that above-described embodiment 2,3,4 and comparative example 2,3,4 are made and rare earth modified Y zeolite sample carry out respectively 2 hours, 4 hours, 8 hours, 17 hours, 24 hours hydrothermal agings under 800 ℃, 100% water vapor conditions to be processed, 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.
From Fig. 1, Fig. 2, can find out, modified Y molecular sieve of the present invention is after hydrothermal aging is processed, and degree of crystallinity and crystallization reservation degree are significantly higher than comparative example.Illustrate that modified Y molecular sieve hydro-thermal structural stability provided by the invention is better.
Test case 3
This example explanation modified Y molecular sieve hydrothermal activity stability of the present invention and coke selectivity.
The sample that above-described embodiment 2,5 and comparative example 2,5 are made carries out respectively 2 hours, 4 hours, 8 hours, 17 hours, 24 hours hydrothermal agings under 800 ℃, 100% water vapor conditions to be processed, measure light oil microactivity (MA), and coke yield, calculate Jiao and turn ratio.The results are shown in Figure 3 and Fig. 4.
Embodiment 6
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different, Z2 molecular sieve replaces with the Z3 molecular sieve of equivalent, is designated as C6.
Embodiment 7
According to the method Kaolinite Preparation of Catalyst of embodiment 1, different, with the Z3 molecular sieve of equivalent, replace Z2 molecular sieve, be designated as C7.
Claims (10)
1. reduce coke yield and produce a catalytic cracking catalyst for gasoline, contain Modified Zeolite Y in butt 10 % by weight ~ 50 % by weight, in butt be no more than the specific Y zeolite containing rare earth of 30 % by weight, in the clay of butt 10 % by weight ~ 70 % by weight with in the inorganic oxide binder of oxide 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%, aluminium oxide is less than 22%, than hydroxyl nest concentration, is less than 0.35mmol/g, described
In formula, M
200 ℃, M
500 ℃and M
800 ℃represent respectively the percent weight loss that sample records when 200 ℃ of temperature, 500 ℃ and 800 ℃, C is sample degree of 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%, than hydroxyl nest concentration, is less than 0.3mmol/g.
3. according to catalytic cracking catalyst claimed in claim 1, it is characterized in that, described catalyst 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 claim 1 ~ 3 any one, the method comprises the Modified Zeolite Y that preparation is described, and prepared Modified Zeolite Y, the described specific Y zeolite containing rare earth, clay and inorganic oxide binder are mixed to making beating and spray-dired step; Described Modified Zeolite Y is to take NaY molecular sieve as raw material, with adopting three exchange operations and three hydrothermal treatment consists to obtain containing rare-earth substance and phosphorus containg substances, wherein, containing rare-earth substance and phosphorus containg substances, adopt exchanged form, 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, containing rare-earth substance, beyond a friendship, in arbitrary exchange operation, adds.
5. according to the preparation method of catalytic cracking catalyst claimed in claim 4, it is characterized in that, described exchange operation further comprises and adds dealumination agent to carry out chemical dealuminization to promote removing of aluminium, and chemical dealuminization process is carried out in arbitrary exchange operation beyond a friendship.
6. according to the preparation method of catalytic cracking catalyst claimed in claim 4, it is characterized in that, described phosphorus containg substances is selected from one or more in orthophosphoric acid, phosphorous acid, pyrophosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and aluminum phosphate.
7. according to the preparation method of catalytic cracking catalyst claimed in claim 4, it is characterized in that, described containing rare-earth substance, be selected from one or more in lanthana, cerium oxide, lanthanum nitrate, cerous nitrate, lanthanum chloride, cerium chloride, nitric acid mishmetal and chlorination mishmetal.
8. according to the preparation method of catalytic cracking catalyst claimed in claim 5, it is characterized in that, described dealumination agent is selected from one or more in ethylenediamine tetra-acetic acid, oxalic acid, citric acid, sulfosalicylic acid, fluosilicic acid, hydrochloric acid, sulfuric acid, nitric acid, ammonium oxalate, ammonium fluoride, ammonium fluosilicate, ammonium fluoroborate.
9. according to the preparation method of the catalytic cracking catalyst described in claim 4～8 any one, 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 ratio of water=1:0.4～1.0:0～0.04:5～10 is mixed to get slurries, by the pH value of inorganic acid adjusting slurry, be 3.0～4.5, then at 70 ℃～95 ℃, process at least and wash after 0.5h, wherein, NaY molecular sieve is in butt, and phosphorus ammonium salt is in elemental phosphorous;
2) product step 1) being obtained under 350 ℃～650 ℃ of temperature, 1%～100% steam atmosphere roasting at least 0.5h obtain a roasting molecular sieve;
3) by step 2) roasting molecular sieve and the phosphoric acid that obtains, dealumination agent is according to a roasting molecular sieve: phosphoric acid: dealumination agent: the ratio of water=1:0～0.04:0.02～0.3:5～10 is mixed, with inorganic acid adjust pH 2.4～3.5, then at 50 ℃～90 ℃, process at least 0.5 hour, filter, wash, washing water temperature >=50 ℃, wherein, a roasting molecular sieve is in butt, and phosphoric acid is in elemental phosphorous;
4) product step 3) being obtained is 350 ℃～650 ℃ of temperature, under 1%～100% steam atmosphere roasting at least 0.5h obtain two roasting molecular sieves;
5) two roasting molecular sieves and the rare earth chlorides that step 4) obtained and water are according to two roasting molecular sieves: rare earth chloride: the ratio of water=1:0.01～0.05:5～10 is mixed, then processing at least 0.5 hour at 70 ℃～90 ℃, filtration; Washing, washing water temperature>=50 ℃, wherein, two roasting molecular sieves are in butt, and rare earth chloride is with RE
2o
3meter;
6) product step 5) being obtained under 350 ℃～650 ℃, 1%～100% steam atmosphere roasting at least 0.5h obtain Modified Zeolite Y.
10. according to the preparation method of the catalytic cracking catalyst described in claim 4 or 9, it is characterized in that, described binding agent is selected from one or more in gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite (Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite) or bayerite (Bayerite); Described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.
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| CN201210217714.9A CN103506153B (en) | 2012-06-27 | 2012-06-27 | Catalytic cracking catalyst for reducing coke yield and producing gasoline |
| PCT/CN2013/000770 WO2014000423A1 (en) | 2012-06-27 | 2013-06-27 | Catalytic cracking catalyst containing modified y type molecular sieve and preparation method therefor |
| AU2013284234A AU2013284234B2 (en) | 2012-06-27 | 2013-06-27 | Catalytic cracking catalyst containing modified Y type molecular sieve and preparation method therefor |
| TW102123065A TWI554604B (en) | 2012-06-27 | 2013-06-27 | Catalytic cracking catalyst includes modified Y zeolite and preparation method thereof |
| KR1020157002100A KR102048326B1 (en) | 2012-06-27 | 2013-06-27 | Catalytic cracking catalyst containing modified y type molecular sieve and preparation method therefor |
| US13/929,044 US9630171B2 (en) | 2012-06-27 | 2013-06-27 | Catalyst containing a modified Y-type zeolite and a preparation process thereof |
| SG11201408778YA SG11201408778YA (en) | 2012-06-27 | 2013-06-27 | Catalytic cracking catalyst containing modified y type molecular sieve and preparation method therefor |
| JP2015518793A JP6232058B2 (en) | 2012-06-27 | 2013-06-27 | Catalytic cracking catalyst containing modified Y-type zeolite and process for its preparation |
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| CN106276961A (en) * | 2015-05-18 | 2017-01-04 | 中国石油化工股份有限公司 | The super steady high silicon rare earth Y type zeolite of little crystal grain gas phase, catalytic cracking catalyst and preparation method thereof and the method for catalytic cracking |
| CN107973315A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of phosphorous and Y molecular sieve of rare earth and preparation method thereof |
| CN107973314A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of phosphorous and Y molecular sieve of rare earth and preparation method thereof |
| CN109970514A (en) * | 2019-03-04 | 2019-07-05 | 宝鸡文理学院 | A kind of method that catalytic refining methanol method synthesizes phenol in methyl phenyl ethers anisole technique |
| CN110835114A (en) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
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