CN102049291B - Hydrocarbon catalytic cracking catalyst and preparation method thereof - Google Patents
Hydrocarbon catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN102049291B CN102049291B CN 200910237004 CN200910237004A CN102049291B CN 102049291 B CN102049291 B CN 102049291B CN 200910237004 CN200910237004 CN 200910237004 CN 200910237004 A CN200910237004 A CN 200910237004A CN 102049291 B CN102049291 B CN 102049291B
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Abstract
A hydrocarbon catalytic cracking catalyst is characterized in that in terms of 100wt% of the catalyst, the catalyst comprises 30-80wt% of molecular sieve and 10-65wt% clay; the catalyst comprises 5.0-20.0wt% of P calculated in the form of P2O5, and 0-1.0wt% of La2O3; P in the catalyst is provided by aluminium phosphate sol; and the aluminium phosphate sol adopted by the catalyst comprises 2-10wt% of AI and 5-15wt% of P, wherein the pH of the aluminium phosphate sol is 1.0-2.5, and the aluminium phosphate sol comprises 2-20wt% of P calculated in the form of HNO3. The prepared hydrocarbon catalytic cracking catalyst has great strength and high activity, can be used as an auxiliary to be mixed with a main catalyst, hardly reduces the activity of the main catalyst, can improve product distribution, has excellent selectivity for dry gas and coke, and meanwhile can improve the yield of light oil.
Description
Technical field
The present invention relates to a kind of catalytic cracking petroleum hydrocarbons Catalysts and its preparation method, specifically relate to a kind of hydrocarbon cracking catalyzer that contains the high silica alumina ratio molecular sieve take aluminium phosphate sol as binding agent and preparation method thereof.
Background technology
Catalytic cracking is the important process technology that petroleum refining industry produces gasoline, diesel oil, liquefied gas, and catalyst or auxiliary agent are one of its core technologies.Catalyst is prepared by the various ingredients except active component usually, and for example, catalytic active component Y type, ZSM-5 molecular sieve, clay, other inorganic oxide etc., phosphorus then often are used to molecular sieves stabilized or improve the scuff resistance of catalyst.Phosphorous hydrocarbon cracking catalyzer mainly contains following three types: a class is that the molecular sieve component of catalyst is phosphorous zeolite molecular sieve, and such as US 5312792, US 5472594, and EP667185 etc. describe; A class is to contain aluminum phosphate or aluminium oxide in the catalyst again, and aluminum phosphate is as the part of matrix or matrix, the Heat stability is good of this class catalyst substrates, activity and selectivity is better, is suitable for the mink cell focus cracking, such as US4158621, US 4179358, US4210560, and US4222896 etc. describe; Another kind of is to process molecular sieve, matrix, binding agent or catalyst with phosphoric acid, phosphorous acid and ammonium salt thereof in catalyst preparation process, with the activity of improving catalyst, selective, hydrothermal stability, preventing from heavy metal pollution ability and mechanical strength, as processing aluminium oxide with ammonium dihydrogen phosphate (ADP), dihydrogen phosphite ammonium etc. among US4567152 and the US4584091, again phosphorus-containing alumina is mixed the spray-dried catalyst that makes with ultrastable, silicon-aluminum sol and clay-phase.
Report adopts colloidal sol containing chloride and aluminium and phosphorated aluminiferous collosol hybrid adhesive among the CN 1180059C, and resulting catalyst can improve product selectivity.
Among the US 5993645 microspherical catalyst after the spray-drying is flooded with phosphate or phosphite, the catalyst after the roasting has preferably preventing from heavy metal performance.
Be reported in the aging boehmite among the CN 86104860A and add phosphoric acid solution, mix with zeolite and clay again, spray-drying, roasting, resulting catalyst abrasion rate descends to some extent.
Scuff resistance is one of important indicator of weighing the Cracking catalyst performance.For this reason, at molecular sieve type particularly in the Cracking catalyst of macromolecule sieve content, the good aluminium colloidal sol of adhesive property commonly used is as binding agent.Usually aluminium colloidal sol refers to aluminium chloride, but use this aluminium colloidal sol band to serve problem, namely when it is used as the binding agent of Cracking catalyst, because higher chlorinity, a large amount of hydrogen chloride gas of in catalyst spray drying forming process, can overflowing, thereby etching apparatus and cause environmental pollution; If after spray-drying, catalyst is not carried out the dechlorination step, chloride catalyst has in catalytic cracking unit in the presence of the water vapour, the hydrogen chloride gas that forms plays destruction to the lattice of molecular sieve in the Cracking catalyst, the active of catalyst significantly descended, and can etching apparatus, enter the severe contamination that causes environment behind the atmosphere.
For the content of chlorine in reducing take conventional aluminium colloidal sol as the catalyst of binding agent, US4458023 has increased calcination steps after the spray-drying in the molecular sieve cracking catalyst manufacture process, and the chlorine in the catalyst is overflowed with the hydrogen chloride form.The shortcoming of the method is that hydrogen chloride has the heavy corrosion effect to roasting apparatus, and surrounding environment is had pollution.
US4542118 contacts to the dechlorination employing ammonia of aluminium colloidal sol Cracking catalyst and the catalyst after the spray-drying, makes wherein hydrogen chloride and ammonia effect generate ammonium chloride, washes with water and removes.Equipment when still there is spray-drying in the method has corrosion and problem of environmental pollution, and operates also more complicated.
US3544476 discloses a kind of binding agent of phosphorous and aluminium, and its preparation method is that metallic aluminium powder is added in the hydrochloric acid solution, is adding phosphoric acid behind 90 ℃ of lower reaction 2h again, then at 80 ℃ of lower aging 30min.Products obtained therefrom consists of: Al 7.0 heavy %, Cl 11.22 heavy %, basicity 59.4% (quite Al/Cl is 0.62: 1), P0
46.1 heavy % (quite P 1.99 heavy %).
US4629717 discloses a kind of method of producing the phosphorus modified aluminas of high surface, that metallic aluminium powder and hydrochloric acid are generated aluminium colloidal sol 102 ℃ of lower reactions, then phosphide is added in the aluminium colloidal sol, add suitable quantity of water again, making aluminium oxide and aluminum phosphate solid content therein is 25-30%.
A kind of preparation method of phosphorated aluminiferous collosol is disclosed respectively among CN1070384A, CN1070385A, CN1317448A and the CN1417296A.The preparation method that CN1070384 provides is: orthophosphoric acid or aluminium dihydrogen phosphate are added in the colloidal sol containing chloride and aluminium, then make phosphorated aluminiferous collosol through high temperature depolymerization, the step such as concentrated.The preparation method that CN1070385A provides is: with metallic aluminium, hydrochloric acid (or aluminium chloride) and orthophosphoric acid (or aluminium dihydrogen phosphate) mixed liquor react under certain conditions, high temperature depolymerization, concentrated and make phosphorated aluminiferous collosol.The preparation method that CN1417296A provides is: can be dispersed into the slurries that solid content is 15～35 % by weight by the aluminium hydroxide of sour peptization or aluminium oxide and the making beating of decationizing water with a kind of, stir lower in these slurries the part by weight adding SPA according to P/A1=1.2～6, then be warming up to 65～95 ℃, and under this temperature, react 15～90min, until become transparent colloid.Be that its part is replaced colloidal sol containing chloride and aluminium during use, to reduce in the slurry before the spray-drying and the content of chlorine on the spray-drying rear catalyst, reduce the discharging of hydrogen chloride gas in the spray-drying tail gas, simplify the washing process of catalyst.Adopt the phosphorated aluminiferous collosol of these method preparations necessarily to be improved as the scuff resistance of the Cracking catalyst of binding agent preparation, but the activity of prepared catalyst all decrease.Although the phosphorated aluminiferous collosol that provides of CN1417296A is not chloride in addition, but during its Kaolinite Preparation of Catalyst owing to mix use with colloidal sol containing chloride and aluminium, make in the slurry before the spray-drying and still contain inevitably a large amount of chlorine on the spray-drying rear catalyst, cause equipment corrosion and problem of environmental pollution still to exist.
The preparation method that CN1317448A provides is: at colloidal sol containing chloride and aluminium (Al
2O
3Content is 15～24 % by weight, and Cl/Al (weight) is than being 1.1～1.7) in add a certain amount of phosphorus and rare earth compound, reaction obtains aluminium colloidal sol and consists of: Al
2O
3Content is 15～24 % by weight, and Cl/Al (weight) is than being 1.1～1.7, P
2O
5/ Al
2O
3(weight) is 0.04～0.5.Although the aluminium colloidal sol of this method modification increases catalyst activity, but same because aluminium colloidal sol contains a large amount of chlorine, make in the slurry before the spray-drying and still contain inevitably chlorine on the spray-drying rear catalyst, cause equipment corrosion and problem of environmental pollution still to exist.
Summary of the invention
The purpose of this invention is to provide a kind of hydrocarbon cracking catalyzer that contains the high silica alumina ratio molecular sieve take aluminium phosphate sol as binding agent and preparation method thereof.This phosphorous hydrocarbon cracking catalyzer has better scuff resistance, and has high activity more, lower dry gas and coke yield, and light oil yield improves, or productivity of propylene improves, octane number improves.
The invention provides a kind of catalyst and cracking of hydrocarbon, is 100% by total catalyst weight, contains the molecular sieve of 30～80 % by weight, and the clay of 10～65 % by weight, contains P in the catalyst, with P
2O
5Count 5.0～20.0 % by weight, be preferably 7.0～15.0 % by weight, La
2O
3Content be 0～1.0 % by weight; P in the catalyst is provided by aluminium phosphate sol, and this aluminium phosphate sol contains the Al of 2～10 % by weight and the P of 5～15 % by weight, and its P/Al weight ratio is preferably 1.3～2.8, and preferred P/Al weight ratio is that 1.5～2.2, pH is 1.0～2.5, with HNO
3Meter, content is 2～20 % by weight, dissolved adhesiveness (25 ℃) is 10～800mPas, preferably 30～300mPas.
The predecessor of P in the catalyst---aluminium phosphate sol preferably prepares by the following method: a kind of predecessor of acid soluble aluminium and the making beating of decationizing water are dispersed into the slurries that solid content is 10～35 % by weight, and stirring the lower concentration that adds in these slurries is 60～98% phosphoric acid (preferably the part by weight according to P/Al=1.3～2.8 adds) and to add concentration be that 40～98% nitric acid is (preferably according to HNO
3/ Al
2O
3=0.2～2.0 part by weight), namely get aluminium phosphate sol after the reaction.Large calorimetric is emitted in this reaction, and temperature reaches 60～90 ℃, just can generate colorless transparent viscous liquid after several minutes.Certain the present invention does not get rid of other method of use yet and obtains this aluminium phosphate sol.
Specific aluminium phosphate sol among the present invention mainly adds as binding agent, and P is provided simultaneously.All the other compositions of catalyst generally determine that according to the composition of prior art PetroChina Company Limited. hydro carbons Cracking catalyst the present invention has no particular limits it, and the below will be to the explanation of their property enumerated.
Said molecular sieve is preferably the molecular sieve of high silica alumina ratio in the catalyst provided by the invention, silica alumina ratio is greater than 10 molecular sieve, such as USY molecular sieve, ZSM type zeolite, BETA zeolite, EU-1 zeolite, modenite, natural zeolite, can be wherein one or more, these molecular sieves can also be the products through rare earth ion or other cation exchange.
Wherein the predecessor of said acid soluble aluminium can be one or more in aluminium powder, ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, δ-aluminium oxide, gama-alumina, θ-aluminium oxide, aluminum nitrate, aluminium chloride, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite, the boehmite, most preferably boehmite.
Said clay is the clay that is conventionally used as Cracking catalyst matrix in the catalyst provided by the invention, the present invention has no particular limits it, such as can being kaolin, halloysite, bentonite, montmorillonite, sepiolite, attapulgite, diatomite, synthesis of clay etc., or their mixture.
The present invention is not particularly limited the preparation method of this catalyst, the preparation method that can adopt general catalyst forms the slurries spray shaping as being added to as materials such as the molecular sieve of main component, clay, adhesives in the water, through roasting, or directly through washing, drying, obtain catalyst prod.Whether Na is depended in washing
2If O content is Na
2O is very low, then can not wash.
The present invention also provides a kind of preferred this catalyst and cracking of hydrocarbon preparation method especially, comprise: with molecular sieve, clay respectively water making beating mixed-shaped become slurries, in clay slurry, add aluminium phosphate sol, continue making beating and mix rear adding molecular sieve pulp, then making beating mixes, and makes the catalyst slurry that solid content is 20～50 % by weight, when containing lanthanum in the catalyst, the predecessor of lanthanum is added in the molecular sieve pulp, with gained catalyst pulp spray drying forming; Microspherical catalyst behind the spray shaping can through roasting, perhaps through washing, drying, all can obtain catalyst prod.
The present invention has following advantages because the specific aluminium phosphate sol of employing is binding agent:
Use aluminium phosphate sol of the present invention very good as its stability of binding agent of catalyst, can long preservation and do not affect its adhesive property.Its adhesive property is fine in addition, particularly owing to add the viscosity that nitric acid can reduce binding agent to a great extent, improves liquidity, thereby consumption of binder can suitably reduce, reduce the catalyst manufacturing cost, and can improve the slurry solid content, thereby reduce spray-dired energy consumption.The catalyst preparation process of the inventive method is simple, easily operation.
Usually use colloidal sol containing chloride and aluminium when the preparation of catalyst, as the binding agent of catalyst, the predecessor of phosphorus adds in addition.The phosphorus that the present invention introduces in auxiliary agent with specific aluminium phosphate sol, three kinds of effects of main performance, first, aluminum phosphate can be prepared the good catalyst of intensity as binding agent, and make catalyst preparation process easy, second, the components such as part P and clay form active very low matrix, can reduce the auxiliary agent carbon deposit, the 3rd, another part P (account for total P 15～50%) and molecular sieve effect, the acidity of adjustable change molecular sieve and improve the hydrothermal stability of molecular sieve, and then improve the reactivity worth of catalyst; The phosphorus that alternate manner is introduced generally only has the third effect, and does not have first, second kind effect.
When binding agent is not chloride, can not make when using its Kaolinite Preparation of Catalyst before the spray shaping chloride on the slurry and spray shaping rear catalyst, thereby avoided equipment corrosion and environmental pollution.This adhesive cures temperature is low, just can solidify (solidification temperature of colloidal sol containing chloride and aluminium is generally greater than 300 ℃) below 200 ℃, thus can significantly reduce the spray shaping exhaust temperature, thus greatly reduce energy consumption, reduce the catalyst manufacturing cost.
We studies show that, aluminium phosphate sol is that the matrix activity that makes of binding agent and clay is very low, but take aluminium phosphate sol of the present invention as binding agent with clay and molecular sieve particularly the molecular sieve of high silica alumina ratio be combined the active of catalyst that makes and obviously improve, and carbon deposit is very low, so molecular sieve can be given full play to the selective cracking effect, product distributes.
Catalyst of the present invention can be used as auxiliary agent and major catalyst mixes different substances together use, and the ratio of mixing different substances together is generally 1～15%, compares with conventional auxiliary agent, the characteristics of catalyst promoter of the present invention mainly are that intensity is good, and is few to the major catalyst activity decreased, can improve product and distribute, reduce dry gas and coke yield.
The specific embodiment
The following examples will be described further characteristics of the present invention, but protection scope of the present invention is not subjected to the restriction of these embodiment.
1) Main Analysis evaluation method and standard in the example
1. constituent contents such as sodium, Al, Si, P in the catalyst: the X-fluorescence method is measured.Adopt the Rigaku ZSXPrimus of company type Full-automatic sequential formula sweep type XRF to analyze, operating voltage is 50kV, and electric current is 50mA, the Rh target.Assay is received in oxidation in the solution, atomic absorption spectrophotometry; Phosphorus detection ， Lin Molybdenum acid yellow complex colorimetric method; Alumina content is measured, the EDTA compleximetry;
2. the mensuration of catalyst specific surface (SA), pore volume (PV): low-temperature nitrogen adsorption method;
3. the catalyst abrasion resistance properties is measured: a certain amount of catalyst is put into fixture, and at constant gas blowing down mill 5h, except first hour, rear four hours average abrasion percentage is called the abrasion index of catalyst, unit be % per hour.Method and standard are: gas lift method Q/SYLS0518-2002;
4. dissolved adhesiveness is measured:
Viscosity refers to that internal fluid owing to interior rubbing action hinders a kind of feature that it flows relatively, represents its size (acting on the internal friction of 1 unit are) with viscosity, and unit is handkerchief second (Pas) or milli handkerchief second (mPas).Evaluation method and standard are GB/T265-1988 oil product kinematic viscosity determination method and dynamic viscosity computing method.1Pas=1Ns/m
2=10P (pool)=1CP (centipoise)
5. micro-activity (MA) is estimated: adopt the ASTM-D3907 method.Catalyst is processed 10h in advance under 800 ℃, 100% water vapour condition, with the huge port light diesel fuel as reaction raw materials oil.460 ℃ of reaction temperatures, oil-feed time 70s, catalyst loading amount 2.5～5g, the productive rate of gasoline adopts GC7890 to analyze after the reaction.
6. catalytic cracking reaction selective evaluation: in small fixed flowing bed (FFB) device, carry out catalyst cracking reaction selective evaluation.Motor octane number (MON), research octane number (RON) (RON): adopt the AC multi-dimensional chromatograph GC6890N of company to analyze.Catalyst is processed 10h through under 800 ℃, 100% water vapour condition in advance.Reaction raw materials oil is grand celebration catalytically cracked stock, 500～535 ℃ of reaction temperatures, air speed 12～15h
-1, oil ratio is 5.Feedstock oil character is listed in table 1.
Table 1 grand celebration catalytically cracked stock character
2) raw materials used specification in the example
Boehmite: Shandong Aluminum Plant produces, Al
2O
3Content 63.3 % by weight;
The SB alumina powder: husky rope (sasol) chemical company produces, Al
2O
3Content 73.5 % by weight;
Aluminum nitrate: Al (NO
3)
39H2O, chemical pure, the Beijing Chemical Plant produces;
SPA: chemical pure,＞85 % by weight, the Beijing Chemical Plant produces;
Red fuming nitric acid (RFNA): chemical pure,＞65 % by weight, the Beijing Chemical Plant produces;
Lanthanum nitrate: La (NO
3)
36H
2O analyzes purely, and Tianjin Derain Fine Chemical Works is produced, and is configured to La
2O
3Solution for 103.13g/l;
Diammonium hydrogen phosphate is analyzed purely, and the Beijing Chemical Plant produces;
Ammonium chloride is analyzed purely, and the Beijing Chemical Plant produces;
Decationizing water: pH 2.8～3.2, sodium oxide content＜5ppm;
Kaolin (igloss 15.5%), halloysite (igloss 23.9%), colloidal sol containing chloride and aluminium (Al
2O
3Content 19.8 heavy %, the Cl:9.55 % by weight, Al/Cl weight ratio 1.1: 1, pH 2.90), be qualified industrial goods, Catalyst Factory of Lanzhou Petrochemical Company production;
BETA molecular sieve: n (SiO
2)/n (Al
2O
3)=25, Catalyst Factory, Nankai Univ production;
ZSM-5 molecular sieve: n (SiO
2)/n (Al
2O
3)=25, Catalyst Factory of Lanzhou Petrochemical Company production;
H-EU-1 molecular sieve: n (SiO
2)/n (Al
2O
3)=30, relative crystallinity 〉=95%, Na
2O≤0.5% prepares with reference to CN101054183A (method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder);
Catalyst: the LV-23 agent of the industrial trade mark, Catalyst Factory of Lanzhou Petrochemical Company production.
Embodiment 1
The present embodiment explanation is according to the preparation of the employed a kind of aluminium phosphate sol binding agent of catalyst of the present invention.
4.7 kilograms of boehmites (are contained Al
2O
33 kilograms) and 10.0 kilograms of decationizing water making beating 30min, in slurries, add 9.7 kilogram of 85% SPA under stirring, then add 5.4 kilograms of 68% red fuming nitric acid (RFNA)s, continuation stirring reaction 45min namely makes water white phosphorus aluminium colloidal sol, and its pH is 1.5.By analysis, this aluminium phosphate sol contains P 8.7 % by weight, Al 5.3 % by weight, P/Al (weight)=1.6, HNO
3Content is 12 % by weight, and dissolved adhesiveness (25 ℃) is 40mPas.
Embodiment 2
The preparation of the employed a kind of aluminium phosphate sol binding agent of present embodiment explanation catalyst of the present invention.
With 3.0 kilograms of aluminum nitrate Al (NO
3)
36H
2O adds 4.3 kilograms of water-soluble solutions of decationizing, adds boehmite 967 grams and (contains Al
2O
3612 grams), making beating 40min adds 2.3 kilogram of 90% phosphoric acid under stirring in slurries, continue stirring reaction 50min, namely makes water white aluminium phosphate sol, and its pH is 1.7.By analysis, this aluminium phosphate sol contains P 7.9 % by weight, Al 6.1 % by weight, P/Al (weight)=1.3, HNO
3Content is 14 % by weight, and dissolved adhesiveness (25 ℃) is 56mPas.
Comparative Examples 1
The preparation method who provides by CN1417296A embodiment 1 prepares phosphorous aluminium sol adhesive.
2.9 kilograms of boehmites (are contained Al
2O
31.8 kilogram) with 4.0 kilograms of decationizing water making beating 30min, in slurries, add 9.6 kilogram of 85% SPA under stirring, be warming up to 70 ℃, then under this temperature, react 45min, namely make water white phosphorated aluminiferous collosol, its pH is 1.7.By analysis, this phosphorated aluminiferous collosol contains P 14.7 % by weight, Al 4.7 % by weight, and P/Al (weight)=3.1, dissolved adhesiveness (25 ℃) is 86mPas.
Embodiment 3
The water that adds 1.28 kilograms in 1.21 kilograms of (butt) BETA molecular sieves carries out homogeneous with cutter, makes the BETA molecular sieve pulp.
Under stirring, with 1875g kaolin and the mixed making beating of 2010ml water 30min, 1.2 kilograms of binding agents according to the preparation of the method among the embodiment 1 are added in the kaolin slurry, continue to stir 1h, add the BETA molecular sieve pulp again, stir 2h, the solid content of gained slurry is 38 % by weight.Slurry is through behind the homogeneous, and spray drying forming obtains containing the catalyst of 35 % by weight BETA molecular sieves, is designated as C1.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Embodiment 4
Except binding agent adopted 1.5 kilograms of binding agents according to the preparation of the method among the embodiment 2, the zeolite molecular sieve of catalyst and kaolin content and preparation method and embodiment 3 were identical, and this catalyst is designated as C2.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Embodiment 5
The water that adds 2.2 kilograms in 1.37 kilograms of (butt) BETA molecular sieves carries out homogeneous with cutter, makes the BETA molecular sieve pulp.
Under stirring, with 1459g halloysite and the mixed making beating of 1083ml water 30min, 1.8 kilograms of binding agents according to the preparation of the method among the embodiment 1 are added in the kaolin slurry, continue to stir 1h, add the BETA molecular sieve pulp again, stir 2h, the solid content of gained slurry is 38 % by weight.Slurry is through behind the homogeneous, and spray drying forming namely obtains containing the catalyst of 45 % by weight BETA molecular sieves, is designated as C3.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Embodiment 6
The present embodiment explanation adopts aluminium phosphate sol to prepare molecular sieve cracking catalyst as binding agent according to the present invention.
Except the zeolite molecular sieve employing ZSM-5 of catalyst, binding agent, molecular sieve and kaolin content and preparation method and embodiment 3 are identical, and this catalyst is designated as C4.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Embodiment 7
The present embodiment explanation adopts aluminium phosphate sol to prepare molecular sieve cracking catalyst as binding agent according to the present invention.
The water that adds 1.18 kilograms in 0.35 kilogram of (butt) ZSM-5 and 0.70 kilogram of (butt) BETA molecular sieve carries out homogeneous with cutter, adds La (NO again
3)
3Solution (La
2O
3Be 103.13g/l) 51.5ml, stir 2h, make the mixed molecular sieve slurries.
Except the zeolite molecular sieve employing of catalyst above-mentioned ZSM-5 and BETA (ZSM-5 and BETA are 1: 2) mixed molecular sieve, binding agent, molecular sieve and kaolin content and preparation method and embodiment 3 are identical, and this catalyst is designated as C5.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Embodiment 8
The present embodiment explanation adopts aluminium phosphate sol to prepare molecular sieve cracking catalyst as binding agent according to the present invention.
At first, with reference to CN 101054183A (method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder) embodiment 1 preparation EU-1 molecular sieve.With 60g NaOH (96%) dissolving that is added to the water, add successively again C6 250g, EUO molecular screen primary powder 25g adds thermal agitation in 80 ℃ and fully dissolves and dispersion, is cooled to room temperature; Then with 180g silicon aluminium microsphere (SiO
2/ Al
2O
3=10) and in the premix material of the 320g white carbon adding mentioned solution stir; Add at last in the stainless steel cauldron in 170 ℃ of reaction 64h, get the EU-1 molecular screen primary powder, silica alumina ratio (SiO
2/ Al
2O
3) be 30.
The second, preparation H type EU-1 molecular sieve: with above-mentioned EU-1 molecular screen primary powder in Muffle furnace in 500 ℃ of lower roasting 6h.EU-1 molecular sieve 1000g (butt) pours 15L exchange solution (NH into after getting roasting
4Cl solution 1mol/l), at 95 ℃ of lower 2h that exchange, filters after the exchange, and washing is extremely without Cl
-, at 500 ℃ of lower roasting 3h; Again the molecular sieve after the roasting is poured into the exchange solution (NH of 15L
4Cl solution 1mol/l), at 95 ℃ of lower exchange 2h, filters after the exchange, and washing is without Cl
-, at 500 ℃ of lower roasting 3h, making the H-EU-1 molecular sieve, the relative crystallinity of this molecular sieve is 93%, Na
2O is 0.46wt%, and specific area is 346m
2/ g, pore volume are 0.28cm
3/ g.
The 3rd, prepare catalyst of the present invention.The water that adds 1.18 kilograms in 0.53 kilogram of (butt) above-mentioned H-EU-1 and 0.53 kilogram of (butt) BETA molecular sieve carries out homogeneous with cutter, adds La (NO again
3)
3Solution (La
2O
3Be 103.13g/l) 24.8ml, stir 2h, make the mixed molecular sieve slurries.
Except the zeolite molecular sieve employing H-EU-1 and BETA (EU-1 and BETA are 1: 1) mixed molecular sieve of catalyst, binding agent, molecular sieve and high mountain range scholar's content and preparation method and embodiment 3 are identical, and this catalyst is designated as C6.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Comparative Examples 2
The explanation of this Comparative Examples prepares molecular sieve cracking catalyst take commercially available colloidal sol containing chloride and aluminium as binding agent.
At 1.05 kilograms of (butt) ZSM-5 (SiO
2/ Al
2O
3=28) add 5.3 kilograms water in the molecular sieve, carry out homogeneous with cutter, add the phosphoric acid of 66.5 grams 85%, stir more than 12 hours, filter, washing, 600 ℃ of roastings 2 hours.Make phosphorous ZSM-5 molecular sieve.
Except binding agent adopts 2.27 kilograms of colloidal sol containing chloride and aluminium (Al
2O
3Content 19.8 heavy %, the Cl:9.55 % by weight, Al/Cl weight ratio 1.1: 1, pH 2.90), the zeolite molecular sieve of catalyst adopts outside the above-mentioned phosphorous ZSM-5, molecular sieve and high mountain range scholar's content and preparation method and embodiment 3 are identical, get spray-dired catalyst 500 and restrain in 600 ℃ of roasting 2h, add 2500ml decationizing water, add 8.5 gram diammonium hydrogen phosphates, 60 ℃ are stirred 2h, filter, drying gets catalyst and is designated as CA1.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Comparative Examples 3
This Comparative Examples explanation prepares molecular sieve cracking catalyst take the phosphorated aluminiferous collosol of Comparative Examples 1 preparation as binding agent.
The water that adds 2.4 kilograms in 2.1 kilograms of (butt) BETA molecular sieves carries out homogeneous with cutter, makes the BETA molecular sieve pulp.To stir 1h in 3.35 kilograms high mountain range scholars and the 4.34 kg water adding making beating tank.2.12 kilograms of binding agents according to the preparation of the method in the Comparative Examples 1 are added in the slurries, behind the homogeneous, add molecular sieve pulp, the solid content of slurry is 38 % by weight.Carry out spray-drying behind the homogeneous, namely get the catalyst that contains 35 % by weight BETA molecular sieves, be designated as CA2.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Comparative Examples 4
The method that this Comparative Examples provides according to CN1180059C embodiment 4 prepares the molecular sieve cracking catalyst of phosphorated aluminiferous collosol.
The water that adds 6.1 kilograms in 3.2 kilograms of (butt) BETA molecular sieves carries out homogeneous in homogenizer, make the BETA molecular sieve pulp.2.8 kilograms (butt) high mountain range scholar and 7.7 kg water are added stirring 1h in the making beating tank, add 1.36 kilograms of (butt) boehmites and 0.541 liter of concentrated hydrochloric acid again, continue making beating 20min, this moment, slurry pH value was 1.6.Slurries are warming up to 60 ℃ of aging 1h, and slurry pH value is 3.1.With 1.77 kilograms of phosphorated aluminiferous collosol and 2.35 kilograms of colloidal sol containing chloride and aluminium (Al according to the preparation of the method in the Comparative Examples 1
2O
3The heavy % of content 19.8, the Cl:9.55 % by weight, Al/Cl weight ratio 1.1: 1, pH 2.90) hybrid adhesive adds in the slurries, behind the homogeneous, adds molecular sieve pulp, and the solid content of slurry is 25 % by weight.Carry out spray-drying, 600 ℃ of roasting 2h behind the homogeneous, namely get and contain 40 % by weight BETA molecular sieves, 8 % by weight colloidal sol containing chloride and aluminiums and phosphorated aluminiferous collosol hybrid adhesive are (with Al
2O
3Meter), 35 % by weight kaolin and 17 % by weight boehmites are (with Al
2O
3Meter) catalyst is designated as CA3.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Comparative Examples 5
The explanation of this Comparative Examples adopts aluminium phosphate sol to prepare molecular sieve cracking catalyst as binding agent according to the present invention.But the P/Al weight ratio of aluminum phosphate is 0.9, not in preferable range of the present invention.
4.7 kilograms of boehmites (are contained Al
2O
33 kilograms) and 12.4 kilograms of decationizing water making beating 30min, in slurries, add 6.5 kilograms of SPAs under stirring, then add 5.9 kilograms in 65% nitric acid, continuation stirring reaction 45min namely makes water white phosphorus aluminium colloidal sol, and its pH is 1.3.By analysis, this aluminium phosphate sol contains the P7.0 % by weight, the Al7.8 % by weight, and P/Al (weight)=0.9, colloid viscosity (25 ℃) is 4500mPas.
The water that adds 3.9 kilograms in 2.1 kilograms of (butt) BETA molecular sieves carries out homogeneous with cutter, makes the BETA molecular sieve pulp.
Under stirring, 23.9%) and the mixed making beating of 2847ml water 30min with the (igloss: of 4.3 kilograms halloysites, 2.0 kilograms of binding agents that prepare are according to the method described above added in the halloysite slurries, continue to stir 1h, add again the BETA molecular sieve pulp, stir 2h, the solid content of gained slurry is 38 % by weight.Slurry is through behind the homogeneous, and spray shaping is dry, obtains containing the catalyst of 35 % by weight BETA molecular sieves, is designated as CA4.The composition of catalyst, physico-chemical property and micro-activity see Table 2.
Data from table 2 can be found out, catalyst CA1 (Comparative Examples 2) as the binding agent preparation compares with the catalyst CA2 (Comparative Examples 3) of the phosphorated aluminiferous collosol that uses prior art (CN1417296A) to obtain as the binding agent preparation with commercially available colloidal sol containing chloride and aluminium, adopts aluminium phosphate sol all obviously to improve as the catalyst activity of binding agent preparation.Compare with the catalyst CA3 of phosphorated aluminiferous collosol used in the Comparative Examples 4 and the preparation of commercially available colloidal sol containing chloride and aluminium hybrid adhesive, the catalyst pulp of the inventive method preparation not only can be not chloride, and the slurry solid content increases substantially, and can reach 42 % by weight (improving 17 percentage points).Catalyst C3 intensity was still fine when improved strength, particularly molecular sieve content were 45 % by weight, and activity is also high.The catalyst CA4 of Comparative Examples 5 is because the P/Al weight ratio of used aluminum phosphate is 0.9, not in preferable range of the present invention, so the activity of catalyst is lower.The phosphorated aluminiferous collosol preparation method of Comparative Examples 1 is similar to the present invention, but P/Al is than in the scope of the invention, and using method (Comparative Examples 4) is also different from the present invention; Comparative Examples 3 usings method are identical with the present invention, although gained catalyst CA2 intensity is good, its activity is lower.
By small fixed flowing bed (FFB) to catalyst cracking reaction selectively evaluate, the result is as shown in table 3.
Major catalyst LV-23 and embodiment 3,6,8 and the catalyst (C1, C4, C6, CA1, CA3) of Comparative Examples 2,4 preparations respectively behind the aging 10h of 800 ℃, 100% steam, C1, C4, C6, CA1, CA3 are mixed different substances together as auxiliary agent and major catalyst LV-23 respectively, and the ratio of doping is 10%.Data result in the table 3 shows: hydrocarbon cracking catalyzer C1 provided by the present invention (take BETA as active component) compares with CA3 has good dry gas, coke selectivity, and light oil yield improves simultaneously; Hydrocarbon cracking catalyzer C4 provided by the present invention (take ZSM-5 as active component) compares with CA1 has good dry gas, coke selectivity, and octane number improves simultaneously.Catalyst C6 (take BETA+EU-1 as active component) also shows good product and distributes, and namely dry gas, coke yield are low, and octane number improves simultaneously.
Table 3 catalyst fixed fluidized bed (FFB) evaluation result
Claims (14)
1. a catalyst and cracking of hydrocarbon is characterized in that by total catalyst weight be 100%, contains the molecular sieve of 30～80 % by weight, and the clay of 10～65 % by weight, contains P in the catalyst, with P
2O
5Count 5.0～20.0 % by weight, La
2O
3Content be 0～1.0 % by weight; P in the catalyst is provided by aluminium phosphate sol, and this aluminium phosphate sol contains the Al of 2～10 % by weight and the P of 5～15 % by weight, and pH is 1.0～2.5, with HNO
3Meter, content is 2～20 % by weight, dissolved adhesiveness is 10～800mPas in the time of 25 ℃; Wherein aluminium phosphate sol prepares by the following method: a kind of predecessor of acid soluble aluminium and the making beating of decationizing water are dispersed into the slurries that solid content is 10～35 % by weight, and stirring the lower concentration that adds in these slurries is 60～98% phosphoric acid and according to HNO
3/ Al
2O
3=0.2～2.0 part by weight adding concentration is 40～98% nitric acid, namely gets aluminium phosphate sol after the reaction.
2. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that in the aluminium phosphate sol, and the P/Al weight ratio is 1.3～2.8.
3. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that in the aluminium phosphate sol, and the P/Al weight ratio is 1.5～2.2.
4. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that in the aluminium phosphate sol not chloride.
5. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that containing P in the catalyst, with P
2O
5Meter, content is 7.0～15.0 % by weight.
6. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that dissolved adhesiveness is 30～300mPas in the time of 25 ℃.
7. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that molecular sieve is that silica alumina ratio is greater than 10.
8. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that in USY molecular sieve, ZSM type zeolite, BETA zeolite, EU-1 zeolite, modenite, natural zeolite one or more of molecular screening.
9. catalyst and cracking of hydrocarbon according to claim 8 is characterized in that molecular sieve is the molecular sieve through rare earth ion or other cation exchange.
10. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that clay is to be selected from kaolin, halloysite, bentonite, montmorillonite, sepiolite, attapulgite, diatomite, the synthesis of clay one or more.
11. catalyst and cracking of hydrocarbon according to claim 1 is characterized in that clay is kaolin.
12. catalyst and cracking of hydrocarbon according to claim 1, the predecessor that it is characterized in that acid soluble aluminium is selected from one or more in aluminium powder, ρ-aluminium oxide, x-aluminium oxide, η-aluminium oxide, δ-aluminium oxide, gama-alumina, θ-aluminium oxide, aluminum nitrate, aluminium chloride, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite, the boehmite.
13. catalyst and cracking of hydrocarbon according to claim 1, the predecessor that it is characterized in that acid soluble aluminium is boehmite.
14. the preparation method of a catalyst and cracking of hydrocarbon claimed in claim 1, it is characterized in that the preparation method comprises: with molecular sieve, clay respectively water making beating mixed-shaped become slurries, in clay slurry, add aluminium phosphate sol, continue making beating and mix rear adding molecular sieve pulp, then making beating mixes, make the catalyst slurry that solid content is 20～50 % by weight, when containing lanthanum in the catalyst, the predecessor of lanthanum is added in the molecular sieve pulp, with gained catalyst pulp spray drying forming; Microspherical catalyst behind the spray shaping can be again through roasting; Perhaps through washing, drying, all can obtain catalyst prod.
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| CN102851058B (en) * | 2011-06-30 | 2015-05-20 | 中国石油天然气股份有限公司 | Method for increasing octane number of catalytically cracked gasoline |
| CN102847547B (en) * | 2011-06-30 | 2014-05-28 | 中国石油化工股份有限公司 | Inorganic binder containing phosphorus and aluminum compounds |
| CN102861606B (en) * | 2011-07-07 | 2014-04-16 | 中国石油化工股份有限公司 | Double-micropore composite molecular sieve, preparation method of double-micropore composite molecular sieve and application of double-micropore composite molecular sieve |
| CN103254925B (en) * | 2013-06-03 | 2015-04-08 | 湖北赛因化工有限公司 | Catalytic cracking propylene assistant and preparation method thereof |
| CN106140252A (en) * | 2015-04-17 | 2016-11-23 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and its preparation method and application |
| CN106732746B (en) * | 2016-12-07 | 2019-10-18 | 四川润和催化新材料股份有限公司 | A method of no ammonia process prepares catalytic cracking catalyst |
| US11319424B2 (en) * | 2019-09-09 | 2022-05-03 | Basell Poliolefine Italia S.R.L. | Plastic depolymerization using halloysite |
| CN114931971B (en) * | 2022-04-26 | 2023-11-14 | 榆林学院 | Nickel nanocluster loaded intergranular mesoporous zeolite catalyst and preparation method and application thereof |
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| US6355591B1 (en) * | 2000-01-03 | 2002-03-12 | Indian Oil Corporation Limited | Process for the preparation of fluid catalytic cracking catalyst additive composition |
| CN1417295A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst containing phosphorus and its prepn |
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| US5194412A (en) * | 1991-01-22 | 1993-03-16 | W. R. Grace & Co.-Conn. | Catalytic compositions |
| US6355591B1 (en) * | 2000-01-03 | 2002-03-12 | Indian Oil Corporation Limited | Process for the preparation of fluid catalytic cracking catalyst additive composition |
| CN1417295A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst containing phosphorus and its prepn |
| CN1506443A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Olefin cracking catalyst resulting in high diesel oil yield and its prepn |
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