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CN1072030C - Phosphorus-contained octahedro zeolite hydrocarbons cracking catalyst and preparation method therefor - Google Patents

Phosphorus-contained octahedro zeolite hydrocarbons cracking catalyst and preparation method therefor Download PDF

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CN1072030C
CN1072030C CN97120271A CN97120271A CN1072030C CN 1072030 C CN1072030 C CN 1072030C CN 97120271 A CN97120271 A CN 97120271A CN 97120271 A CN97120271 A CN 97120271A CN 1072030 C CN1072030 C CN 1072030C
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heavy
catalyzer
faujusite
rare earth
boehmite
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CN1217231A (en
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张剑秋
田辉平
张蔚琳
范中碧
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

一种含磷八面沸石烃类裂化催化剂，它含有八面沸石10～60重%、磷0.01～1.5重%、稀土氧化物0.1～40重%、铝粘结剂(以氧化铝计)10～60重%、粘土0～75重%，所述铝粘结剂分别来自拟薄水铝石和铝溶胶，以氧化铝计，来自拟薄水铝石和铝溶胶的铝粘结剂的重量比为0.1～10，所述含磷八面沸石是将八面沸石与含磷化合物水溶液混合均匀后，干燥，于450～600℃焙烧0.5小时以上制备的。A phosphorus-containing faujasite hydrocarbon cracking catalyst, which contains 10-60% by weight of faujasite, 0.01-1.5% by weight of phosphorus, 0.1-40% by weight of rare earth oxides, and 10% of aluminum binder (calculated as alumina) ～60% by weight, clay 0～75% by weight, the aluminum binder comes from pseudo-boehmite and alumina sol respectively, in terms of alumina, the weight ratio of the aluminum binder from pseudo-boehmite and alumina sol is 0.1 to 10. The phosphorus-containing faujasite is prepared by uniformly mixing the faujasite and the aqueous solution of the phosphorus-containing compound, drying, and calcining at 450-600° C. for more than 0.5 hours.

Description

Phosphorous faujusite hydrocarbon cracking catalyzer and preparation method thereof
The invention relates to hydrocarbon cracking catalyzer that contains faujusite and preparation method thereof, more specifically say so about phosphorous faujusite hydrocarbon cracking catalyzer and preparation method thereof.
The existing a lot of reports of cracking catalyst of phosphorous and zeolite and preparation method thereof.
US4,970,183 disclose a kind of hydrocarbon cracking catalyzer composite, it contains a kind of granular mixture, this mixture by 95～50 heavy % not phosphorated porous matrix and 5～50 heavy % phosphorated Y type faujusites form, with P 2O 5Account for the weight meter of Y type faujusite, phosphorous 0.3～15 heavy % in the Y type faujusite.Described phosphorus-contained gamma-type faujusite is contacted with a kind of P contained compound by Y type faujusite, introducing phosphorus, and in water vapour atmosphere, has introduced the y-type zeolite of phosphorus and makes in 400～800 ℃ of heating.This catalyzer has higher active and to the selectivity of gasoline when having than high hydrothermal stability.
EP252,761A2 disclose a kind of catalyzer, and this catalyzer contains a kind of nonzeolite inorganic oxide matrix and a kind of overstable gamma zeolite, and described zeolite makes it contain the phosphorus of significant quantity with a kind of sufficiently long time of P contained compound pre-treatment.Described pre-treatment is that zeolite is contacted with P contained compound, the medium of contact is phosphorous liquid medium (as a water), pH value is 2.0～8.0, phosphorus content in the medium is 0.05～5 heavy %, the contact temperature is 60～250 °F (15.6～121.1 ℃), zeolite before handling with phosphorus was at 1000～1600 °F, with 5%～100% steam-treated 15 minutes to 100 hours.This catalyzer has lower coke yield.
EP397,183A discloses a kind of zeolite compositions and preparation method thereof, and said composition contains (a) and contains 2～5 heavy %Na 2The NaY of the ion-exchange of O is (b) with P 2O 5Meter, the phosphorus of 0.1～4.0 heavy %.The preparation method of this zeolite compositions comprises the NaY zeolite with about 24.63～24.72 dusts of structure cell diameter, with ammonium salt solution exchange, and with ammonium salt solution and water washing, obtains the part exchange, contains 1.0～5.0 heavy %, preferred 2.5～4.5 weight %Na 2The NaHNH of O 4Y; With the NaHNH that obtains 4Y zeolite and a kind of phosphorous aqueous solution mix under the condition of PH about 4～7, and in 20～350 ℃ of oven dry, preferably spraying drying obtains a kind of phosphorous 0.1～4 heavy %, the NaHNH of preferred 0.7～2 heavy % 4Y zeolite P/NaHNH 4Y; With P/NaHNH 4Y zeolite is (moisture vapor 10～100%) in the presence of water vapor, in 500～700 ℃ of heating 0.5～2 hour, obtains a kind of structure cell diameter 24.45～24.60 dusts, the P/USY zeolite of preferred 24.52～24.58 dusts.The catalyzer that contains this P/USY zeolite has higher cracking activity and to the selectivity of gasoline.
US5,110,776 disclose a kind of preparation method who contains the cracking catalyst of zeolite, this method comprises that (a) comes modified zeolite by handling zeolite with the phosphatic aqueous solution, form a kind of aqueous liquid mixture, (b) direct aqueous liquid mixture with phosphorous hydrochlorate modified zeolite mixes with a kind of precursor of carrier, forms a kind of slurries, and (c) the described slurries of spraying drying form catalyzer.Described zeolite comprises large pore zeolite (as X, Y, USY, REX, REY, REUSY, dealuminzation Y, Silicon-rich dealuminzation Y), mesopore zeolite and pore zeolite, preferred REY.Catalyzer with this method preparation has improved abrasion resistance, and under the prerequisite that does not significantly change dry gas and coke growing amount, has improved the octane value of crackate.
CN1,022,465C discloses a kind of phosphorated hydrocarbon cracking catalyzer, and this catalyzer contains 5～50 heavy % zeolites, 20～85 heavy % clays, 0.05～5.0 heavy % phosphorus and 5～35 heavy % (with Al 2O 3Meter) pseudo-boehmite or aluminium sol adhesive, phosphorus wherein is distributed in the surface of granules of catalyst.This Preparation of catalysts method comprises that (1) is with an amount of zeolite, clay and pseudo-boehmite or aluminium colloidal sol mix by the conventional preparation method of hydrocarbon cracking catalyzer, spraying drying, (2) with temperature be 30～70 ℃ ammoniacal liquor, with liquid-solid ratio is (1) step of the consumption washing products therefrom of 10～60 (weight ratios), the pH value of ammoniacal liquor is advisable with the final pH value 4～10 of control slurries, filter, (3) compound concentration is the P contained compound aqueous solution of 0.02～17.5 heavy % (in P), the solution pH value is 0.5～10, under the temperature of room temperature～100 ℃, it in liquid-solid ratio (weight ratio) 0.2～60 ratio, the phosphorous aqueous solution is mixed and continuous the stirring 3～120 minutes with (2) step products therefrom, filter 90～130 ℃ of dryings, this step can repeat 0～5 time, so that the phosphorus on the catalyzer reaches predetermined amount.Described zeolite refers to be used as usually one or more in the various zeolites of catalyst activity component, comprises X type zeolite, y-type zeolite, β zeolite, ZSM type zeolite, mordenite etc.Described clay refers to be commonly used for the various clays of catalyst substrates, as kaolin, halloysite, polynite, sepiolite, concavo-convex handful stone etc.This catalyzer has good abrasive wear resistance, good hydrothermal stability and catalytic activity.
CN1,024,504C discloses a kind of hydrocarbon cracking catalyzer, this catalyzer is by the mixture that is selected from one of HY, HX, REHY, REX or wherein two or more mixture or one of them and other zeolite of 4～50 heavy %, the high temperature resistant phosphorus composition that contains aluminium inorganic oxide and 0.05～4 heavy % of the clay of the natural or synthetic of 0～80 heavy %, 5～95 heavy %.This Preparation of catalysts method comprises Na +The faujusite of pre-exchange degree 0～90% or mixture, clay and the high temperature resistant aluminium inorganic oxide precursor that contains of other zeolite are mixed into glue by predetermined proportion, spray drying forming behind the homogeneous, through or without washing, carry out one or many ion-exchange aftertreatment with the P contained compound aqueous solution, filtration, drying.Described other zeolite is selected from one of USY, REUSY, HZSM, mordenite, L zeolite, β zeolite.Described clay is cracking catalyst matrix kaolin, halloysite, polynite, a wilkinite commonly used.The described high temperature resistant precursor that contains the aluminium inorganic oxide is the thin water aluminium glue of aluminium colloidal sol, plan, silica-alumina gel, Al 2O 3MgO glue, Al 2O 3CaO glue or Al 2O 3ZnO 2Glue, or wherein two kinds.This catalyzer has the catalytic activity higher than prior art, abrasive wear resistance and gasoline selective.
CN1,026,217C discloses a kind of hydrocarbon cracking catalyzer of phosphorous and hyperastable Y-type RE zeolite, this catalyzer is by the mixture of the hyperastable Y-type RE zeolite of 1～40 heavy % or itself and ZSM-5 zeolite, the phosphorus of the high-temperature inorganic oxide of the clay of 0～95 heavy %, 0～85 heavy % and 0.1～1.0 heavy % is formed, and wherein the content of rare earth in the hyperastable Y-type RE zeolite is (with RE 2O 3Meter) is 0.5～6.0 heavy %.This Preparation of catalysts method comprises mixes the precursor of zeolite slurry, clay and/or high-temperature inorganic oxide by predetermined proportion, spray drying forming behind the homogeneous carries out one or many ion-exchange aftertreatment, drying with the P contained compound aqueous solution then.Wherein post-treatment condition is, phosphorus solution weight is 1～20 times of catalyzer butt weight, and phosphorus solution concentration is in phosphorus content 0.001～1 heavy %, 5～99 ℃ of temperature, pressure normal pressure, switching process time 1～90 minute.This catalyzer has higher hydrothermal stability, abrasive wear resistance, catalytic activity and to the selectivity of gasoline.
In sum, phosphorous and Catalysts and its preparation method zeolite is mainly the hydrothermal stability that improves catalyzer, catalytic activity and the selectivity of gasoline is designed in the prior art, and these catalyzer are not high enough to the selectivity of diesel oil.The demand of diesel oil increases substantially in recent years, and this just requires us to develop the catalyzer that is fit to high-yield diesel oil.
The objective of the invention is to overcome the existing catalyzer shortcoming not high, a kind of high-yield diesel oil that is suitable for is provided, hydrocarbon cracking catalyzer of phosphorous and faujusite and preparation method thereof the diesel oil selectivity.
Catalyzer provided by the invention contains phosphorous faujusite, al binder and rare earth oxide, contain or argillaceous not, with the total catalyst weight is benchmark, contain faujusite 10～60 heavy % in the catalyzer, phosphorus 0.01～1.5 heavy %, rare earth oxide 0.1～40%, al binder (in aluminum oxide) 10～60 heavy %, clay 0～75 heavy %, described al binder is two kinds of al binders, these two kinds of al binders are respectively from pseudo-boehmite and aluminium colloidal sol, in aluminum oxide, weight ratio from the al binder of pseudo-boehmite and aluminium colloidal sol is 0.1～10, described phosphorous faujusite be with the aqueous solution of faujusite and P contained compound evenly after, drying, roasting prepared more than 0.5 hour.
Preparation of catalysts method provided by the invention comprises
(1) will contain or not contain rare earth, Na 2It is even with the aqueous solution of P contained compound that O content is lower than the faujusite of 5 heavy %, left standstill 0～8 hour, and drying, in 450～600 ℃ of roastings more than 0.5 hour, must the phosphorated faujusite;
(2) phosphorous faujusite is mixed with aluminium colloidal sol and aged pseudo-boehmite slurries, behind the homogeneous in 400～600 ℃ of roastings or spraying drying, in described pseudo-boehmite and the aluminium colloidal sol salic weight ratio be 0.1～10;
(3) wash the product that (2) obtain according to a conventional method.
According to catalyzer provided by the invention, the preferred content of each component is faujusite 20～60 heavy %, al binder 10～60 heavy %, phosphorus 0.3～1.2 heavy %, rare earth oxide 0.5～10 heavy %, clay 0～65 heavy %.
Can contain below the 3.0 heavy % the following Na of preferred 2.5 heavy % in the catalyzer provided by the invention 2O.
The weight ratio preferred 0.5～7.0 of described binding agent from pseudo-boehmite and aluminium colloidal sol.
Described faujusite is selected from X type zeolite, y-type zeolite or its mixture.Described X type zeolite is selected from one or more among Hydrogen X zeolite HX, rare-earth type X zeolite REX or the REHX.Described y-type zeolite is selected from Hydrogen Y zeolite HY, one or more among rare-earth type Y zeolite REY or REHY, ultrastable Y USY, rare-earth type overstable gamma zeolite REUSY, the sealumination modified Y zeolite DASY.Among the preferred HY of described faujusite, REY, REHY, USY, REUSY, the DASY one or more.
Described rare earth oxide can be the mixed rare-earth oxide of rich lanthanum or rich cerium, also can be the single oxide of elements such as lanthanum, cerium, the mixed rare-earth oxide of preferred rich lanthanum or rich cerium.
Described clay is selected from the various clays that are commonly used for catalyst substrates, can be in kaolin, halloysite, polynite, wilkinite, the sepiolite one or more as it, preferred kaolin.
According to Preparation of catalysts method provided by the invention:
Mixing, leaving standstill of the aqueous solution of faujusite (1) and P contained compound can be carried out under 0～100 ℃ temperature, preferably at 0～40 ℃, more preferably at room temperature carries out.
(1) contains rare earth and Na described in 2O content is lower than the faujusite of 5 heavy %, sodium type faujusite can be exchanged and makes with the aqueous solution that contains rare earth ion, also sodium type faujusite can be carried out NH earlier 4 +Ion-exchange exchanges and makes with the aqueous solution that contains rare earth ion again, also can directly be purchased and obtains.Described rare earth and the Na of not containing 2O content is lower than the faujusite of 5 heavy %, sodium type faujusite can be carried out NH 4 +Ion-exchange and making also can be directly commercially available.
Described P contained compound is the phosphorated water-soluble cpds, it is selected from ortho-phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, the ammonium phosphite one or more, more preferably phosphoric acid ammonium, Secondary ammonium phosphate or primary ammonium phosphate.The described P contained compound aqueous solution is in phosphorus content, and its concentration can be 0.1～30 heavy %, preferred 0.5～2.5 heavy %, and P contained compound solution and zeolite weight ratio can change in a big way, and preferred 0.5～5.0.
(1) time of 450～600 ℃ of roastings described in can be longer, but be save energy, preferred 0.5～5 hour of roasting time.
(1) step with phosphorus compound processing faujusite described in can repeat repeatedly.
(1) with the mixing of faujusite and P contained compound solution, when faujusite is two or more, preferably different faujusites is mixed with P contained compound respectively described in.
(2) pseudo-boehmite of aged described in slurries can prepare according to a conventional method, as the making beating of pseudo-boehmite and water after stirring, can use quantitative hcl acidifying, wear out 0.5～3 hour in 50～80 ℃, are prepared into the aged pseudo-boehmite.
(2) contain rare earth compound during the pseudo-boehmite of aged described in slurries are best, its preparation method is: with pseudo-boehmite and water making beating, adding rare earth compound or its solution, after stirring, use quantitative hcl acidifying, wore out 0.5～3 hour in 50～80 ℃, whether rare earth adding quantity wherein can according to containing rare earth in the faujusite and content is regulated, and the rare earth consumption should guarantee that the content of rare earth in the final catalyzer reaches preset value.Water, hydrochloric acid consumption and identical when preparing the aged pseudo-boehmite of compounds containing rare earth not.Described rare earth compound is one or more in the water-solubility rare-earth compound, as rare earth chloride, rare earth nitrate etc., and preferred rare earth chloride.
(2) described in phosphorous faujusite and mixing of aluminium colloidal sol and aged pseudo-boehmite slurries can be carried out in any order, prepare catalyzer argillaceous as need, then clay can add in this step.
When (2) phosphorous faujusite being mixed with aluminium colloidal sol and aged pseudo-boehmite slurries, also can add the not aged pseudo-boehmite of another part, the consumption of this part pseudo-boehmite can account for below the 65 heavy % of used pseudo-boehmite total amount.
The part of the colloidal sol of aluminium (2) can add in (1) step, in other words, also can contain part aluminium colloidal sol in (1) the step mixture, and the amount of this part aluminium colloidal sol can account for below the 55 heavy % of used aluminium colloidal sol total amount.
Owing to adopted two binding agents and preparation method unlike the prior art, when catalyzer provided by the invention is used for heavy oil fluid catalytic cracking, keeping yield of light oil to be not less than under the condition of existing catalyzer, has the existing higher diesel yield of catalyzer, higher diesel and gasoline ratio, lower gas yield and lower coking yield.The light oil microactivity of catalyzer provided by the invention is also apparently higher than forming close existing catalyzer.For example, with catalyzer provided by the invention at 800 ℃, with 100% steam aging after 17 hours, on continuous micro-reactor, be used for the catalytic cracking boiling range and be 235～335 ℃ solar oil, 460 ℃ of temperature of reaction, weight hourly space velocity 16 hours-1, agent weight of oil are than under 3.2 the condition, and its light oil microactivity all is higher than forms close existing catalyzer.Again for example, with catalyzer provided by the invention 800 ℃ with 100% steam aging after 4 hours, on micro-reactor continuously, be the catalyzer of 227～475 ℃ decompressed wax oil as the catalytic cracking boiling range, 482 ℃ of temperature of reaction, weight hourly space velocity 16 hours -1Under the condition of agent-oil ratio 4.0, adopt catalyzer provided by the invention, have and be not less than the yield of light oil of forming close existing catalyzer at least, compare with forming close existing catalyzer, catalyzer provided by the invention has higher diesel yield and diesel and gasoline ratio, lower gas recovery ratio and is not higher than the coking yield of existing catalyzer at least.
The following examples will the present invention will be further described.
Used zeolite is Zhou village, Shandong catalyst plant product in the example, wherein contains RE in the REHY zeolite 2O 33.6 heavy %, Na 2O content 4.5 heavy %, silica alumina ratio is 5.6; Contain RE in the REY zeolite 2O 319.5 heavy %, Na 2O content 1.6 heavy %, silica alumina ratio is 5.4; Contain Na in the USY zeolite 2O is 0.87 heavy %, and silica alumina ratio is 6.8; Contain Na in the REUSY zeolite 2O 1.2 heavy %, RE 2O 31.5 heavy %, silica alumina ratio 6.8; The DASY zeolite contains Na 2O 0.98 heavy %, silica alumina ratio is 6.2; Contain Na in the HY zeolite 2O 0.68 heavy %, silica alumina ratio is 5.6, this HY zeolite is the NaY zeolite (Na that same producer produces 2The heavy % of O content 11, silica alumina ratio 5.6) in the 0.15M aqueous ammonium chloride solution, in the exchange 1 hour down of 60 ℃ of liquid-solid ratioes 20, temperature, filter, to there not being chlorion, drying in 550 ℃ of roastings 2 hours, exchanges roasting 3 times and preparation altogether with deionized water wash.
Zeolite in the catalyzer, al binder, kaolin content are got by calculating, phosphorus (P), rare earth (RE 2O 3) and Na 2O content adopts the x-ray fluorescence spectrometry method to measure.
Used kaolin is China Kaolin Co., Ltd's Industrial products in the example, and its solid content is 85 heavy %; Used pseudo-boehmite is that Shandong Aluminum Plant produces, and its alumina content is 35.0 heavy %, and aluminium colloidal sol is that Zhou village, Shandong catalyst plant is produced, and its alumina content is 21 heavy %.
Example 1～12
Preparation of catalysts provided by the invention.
(1) takes by weighing quantitative REHY, REY, USY, REUSY, HY or/and DASY and quantitative ammonium phosphate (chemical pure, Beijing Chemical Plant's product), Secondary ammonium phosphate (chemical pure, Beijing new Photochemical agents factory product), primary ammonium phosphate (chemical pure, the Beijing Chemical Plant produces) or phosphoric acid (chemical pure, the Beijing Chemical Plant produces) aqueous solution even, leave standstill certain hour or do not leave standstill, after the drying, in 450～600 ℃ of quantitative times of roasting, get phosphorous faujusite.
(2) quantitative pseudo-boehmite and gauge water are mixed, add or do not add quantitative RECl x(Baotou rare earth factory in the Inner Mongol produces, described RECl xAfter 1 hour, measuring rare earth oxide content is RE through 800 ℃ of roastings 2O 3Be 46 heavy %, La 2O 324.5 heavy %, CeO 26.0 heavy %, Pr 6O 36.0 heavy %, Nd 2O 39.5 heavy %) or its aqueous solution even, dropwise add quantitative concentrated hydrochloric acid (chemical pure contains HCl 36～38 heavy %, and the Beijing Chemical Plant produces) again and stir, be warming up to 60～70 ℃, the aging regular hour, the aged pseudo-boehmite.The phosphorous faujusite of (1) step preparation is pulverized, mixed with quantitative kaolin, quantitative aluminium colloidal sol and aged pseudo-boehmite, in 500 ℃ or 550 ℃ of roasting regular hours.
(3) product that (2) is obtained is pulverized, and weighs % and NH with 20 times of weight in hydrochloric 0.84 of sample butt down at 60 ℃ respectively 3H 2The acid solution of the heavy % of O 0.62, contain NH 3H 2The alkali lye of the heavy % of O 0.17 and deionized water mix making beating, washing, wash after-filtration at every turn, and the filter cake that obtains at last promptly gets catalyst A～L provided by the invention in 120 ℃ of dryings 2 hours.
Table 1 has provided kind, the consumption of used faujusite of (1) step, P contained compound kind, its strength of solution and consumption.Table 2 has provided time of repose, maturing temperature and the time in (1) step.When table 3 has provided (2) step preparation aged pseudo-boehmite, pseudo-boehmite, water, RECl xOr the consumption and the aged temperature and time of its solution, concentrated hydrochloric acid.Table 4 provided for (2) consumption, maturing temperature and the time that goes on foot used kaolin, aluminium colloidal sol.Table 5 has provided the composition of catalyst A～L.
Comparative Examples 1～12
The preparation of reference catalyst.
Comparative Examples 1～12 is corresponding one by one with example 1～12.
Wherein, the difference of Comparative Examples 1,2,3,4,6,7 and example 1,2,3,4,6,7 has been to omit the step of (1) step with P contained compound processing zeolite, phosphorous faujusite is directly with not phosphorous faujusite replacement accordingly in (2) step, and, described al binder is respectively 45.0 grams, 30.0 grams, 42.0 grams, 45.6 grams, 42.0 grams, 43.0 grams with single al binder pseudo-boehmite, pseudo-boehmite consumption.
Comparative Examples 5 is according to US4, and 970,183 disclosed methods prepare catalyzer: ammonium chloride (chemical pure, the Beijing Chemical Plant produce) solution of 80 gram NaY zeolites (specification is with example 5) with 1600 milliliters of 0.15M is filtered 60 ℃ of exchanges 1 hour, and washing is to there not being Cl -, 550 roastings 2 hours, repeated exchanged and roasting are 2 times again, get Na 2The HY zeolite of O content 0.73 heavy % is with the H of HY zeolite and 30.0 grams, 20 heavy % 3PO 4(the NH of solution and 40.0 grams, 20 heavy % 4) 2SO 4(chemical pure, Tianjin Bazhou City's chemical industry subsidiary factory of quartzy Clock Factory produces) solution mixes, and stirs 0.5 hour down at 90 ℃, and filtration, washing are to there not being SO 4 2-, obtain phosphorous NH 4Y zeolite, at 700 ℃ down with this zeolite of 100% steam-treated 3.5 hours, the product that obtains is phosphorous HY zeolite, earlier with 29.0 gram silicon sol, 20.4 gram kaolin, 14 gram hydrated aluminum oxides (solid content 34.8 heavy %, Shandong Aluminum Plant produces), again with 17.6 the gram phosphorous HY zeolite mix with it, drying, with the exsiccant sample with containing RECl x5.0 the solution impregnation of gram and water 80 grams, washing is to there not being Cl -, drying gets reference catalyst.
Comparative Examples 8 is according to US5, and 110,776 examples, 3 disclosed methods prepare catalyzer: with REY zeolite 75 grams, 0.45 gram dispersion agent, 4.32 gram primary ammonium phosphate and 133.8 gram deionized waters mix, and stir 16 hours, add 163.8 gram deionized waters again, stir, make and contain zeolite slurry.With 88.0 gram kaolin, 482.2 gram water glass (contain SiO 226.8 heavy, Na 2The heavy % of O 7.8, the Zhou village catalyst plant is produced) and 2134 gram deionized waters mix, add the zeolite slurry that contains that has prepared at last, mix, dry, washing is not to there being acid ion, reslurry, spraying drying get reference catalyst.
Comparative Examples 9 is according to EP252,761 disclosed methods prepare catalyzer, 50.0 gram USY zeolites were handled 16 hours at 760 ℃ with 100% water vapor, get zeolite 30.0 grams after the processing, with 1000 milliliters of solution that contain 66.7 gram primary ammonium phosphates, 65～66 ℃ of processing 2 hours down, filtration, drying, in 538 ℃ of roastings two hours, mix with silica-alumina gel 47 grams (butt weight) that contain 25 heavy % aluminum oxide, make reference catalyst.
Comparative Examples 10 is according to example among the CN1022465C 10 preparation catalyzer, be used DASY zeolite be the described DASY zeolite of specification sheets page 5 of the present invention.
Comparative Examples 11 is according to example among the CN1026217C 1 preparation catalyzer, be used NaY zeolite be the described NaY zeolite of specification sheets page 5 of the present invention.
Comparative Examples 12 is according to example among the CN1024504C 3 preparation catalyzer, be used NaY zeolite be the described NaY zeolite of specification sheets page 5 of the present invention.
Table 1
Example number Faujusite The P contained compound aqueous solution
Kind Consumption, gram P contained compound Strength of solution, heavy % Solution usage, gram
1 2 3 4 5 6 7 8 9 10 11 12 REHY REY USY REUSY HY REHY REY REHY REY USY DASY REUSY HY 42.0 24.0 21.0 28.0 25.6 15.0 15.0 18.0 37.5 30.0 33.5 60.0 30.0 Ammonium phosphate ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) ammonium phosphate ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) ammonium dihydrogen phosphate (ADP) monophosphate monophosphate ammonium dihydrogen 6.2 4.8 5.0 7.5 6.2 2.3 2.3 4.2 4.2 4.3 4.0 4.5 4.8 60.0 30.0 30.0 34.0 30.0 40.0 40.0 30.0 51.0 50.0 50.0 60.0 46.0
Table 2
Example number Time of repose, hour Roasting
Temperature, ℃ Time, hour
1 3.0 450 0.5
2 0 500 5.0
3 4.0 550 0.5
4 3.0 600 0.5
5 6.0 500 1.0
6 5.0 500 0.5
7 6.0 450 0.5
8 3.0 500 0.5
9 4.0 500 0.5
10 5.0 480 4.5
11 4.0 600 1.0
12 6.0 500 1.0
Table 3
Example number The pseudo-boehmite consumption, gram Water consumption, gram RECLX or its solution usage, gram The concentrated hydrochloric acid consumption, gram Aging
RECLX, gram Water consumption, gram Temperature, ℃ Time, h
1 30.0 84.0 4.2 10.0 8.5 70 1.5
2 18.0 26.0 0 0 7.0 70 2.0
3 24.0 30.0 4.0 0 10.0 70 1.5
4 30.0 42.0 6.0 0 14.0 70 1.5
5 24.0 30.0 2.8 0 10.0 70 1.5
6 24.0 30.0 4.0 0 10.0 70 1.5
7 25.0 60.0 3.2 0 10.0 70 2.0
8 169.0 400.0 0 0 50.0 70 2.5
9 114.3 320.0 6.0 0 27.4 60 2.0
10 28.6 42.0 5.0 10.0 10.0 60 2.0
11 35.0 50.0 0 0 14.0 60 1.5
12 24.0 30.0 4.0 0 10.0 70 1.5
Table 4
Example number The kaolin consumption, gram Aluminium colloidal sol consumption, gram Roasting
Temperature, ℃ Time, hour
1 2 3 4 5 6 7 8 9 10 11 12 24 30.0 28,0 30.0 30.0 16.0 20.0 44.0 0 99.3 127.0 39.7 25.0 20.0 30.0 26.0 30.0 30.0 30.0 47.6 33.3 29.0 30.0 13.6 500 500 500 500 500 500 500 500 500 500 500 500 2.0 2.0 2.0 1.0 1.5 2.0 3.0 4.0 3.0 3.0 4.0 2.0
Table 5
Example number The catalyzer numbering Catalyzer is formed, heavy % Z *
Zeolite Binding agent Kaolin P RE 2O 3 Na 2O
1 A 47.7 19.5 25.2 0.96 4.27 2.36 2
Comparative Examples 1 A’ 48.2 19.7 25.5 0 4.30 2.30 -
2 B 31.4 17.4 42.2 0.64 7.75 0.64 1.5
Comparative Examples 2 B’ 31.6 17.5 42.5 0 7.80 0.60 -
3 C 33.7 23.8 38.6 0.64 2.97 0.29 1.3
Comparative Examples 3 C’ 33.9 24.0 38.8 0 3.00 0.30 -
4 D 37.44 21.9 35.1 0.73 4.37 0.46 1.9
Comparative Examples 4 D’ 37.72 22.1 35.3 0 4.40 0.47 -
5 E 37.6 21.8 37.7 0.74 1.90 0.25 1.3
Comparative Examples 5 E’ 37.5 21.8 37.9 0.72 1.80 0.28 -
6 F 42.25 24.24 22.43 0.82 8.75 1.51 1.3
Comparative Examples 6 F’ 42.6 24.4 22.6 0 8.84 1.55 -
7 G 31.9 29.0 32.8 0.65 4.09 1.56 1.4
Comparative Examples 7 G’ 32.1 29.2 33.0 0 4.12 1.58 -
8 H 20.4 47.8 25.9 0.39 5.09 0.42 5.9
Comparative Examples 8 H’ 20.5 47.7 25.9 0.40 5.07 0.43 -
9 I 37.02 58.5 0 0.72 3.44 0.32 5.7
Comparative Examples 9 I’ 37.95 60.0 0 1.72 0 0.34 -
10 J 24.24 11.77 61.68 0.39 1.68 0.24 5.3
Comparative Examples 10 J’ 24.66 11.95 62.76 0.38 0 0.25 -
11 K 31.2 10.0 57.5 0.44 0.50 0.37 1.9
Comparative Examples 11 K’ 31.2 9.8 57.7 0.46 0.70 0.14 -
12 L 38.5 14.5 43.6 0.77 2.37 0.26 2.9
Comparative Examples 12 L’ 39.3 14.9 44.5 1.0 0 0.30 -
Example 13
Preparation of catalysts provided by the invention.
(1) 20.0 gram REHY zeolites and 30.0 are restrained ammonium dihydrogen phosphate and the 10.0 gram aluminium colloidal sols that concentration are 4.5 heavy % and mix, left standstill 2 hours, drying was in 500 ℃ of roastings 1 hour.
(2) 30.0 gram pseudo-boehmites and 80.0 gram deionized waters are mixed, add 5.0 gram RECl x, mix, under agitation dropwise add 8.0 gram concentrated hydrochloric acids, be warming up to 60 ℃, aging 2.5 hours, get the aged pseudo-boehmite.The product that (1) obtains is pulverized, mixed with 15.0 gram kaolin, aged pseudo-boehmite and 40.0 gram aluminium colloidal sols, in 500 ℃ of roastings 2 hours.
(3) (3) step that repeats example 1～12 operates, and gets catalyzer M provided by the invention, and the composition of catalyzer M is listed in the table 6.
Example 14
Preparation of catalysts provided by the invention.
(1) is that the ammonium dibasic phosphate solution and 14.0 of 5.3 heavy % restrains the aluminium colloidal sols and mixes with 24.0 gram REUSY zeolites and 35.0 gram concentration, left standstill 5 hours, drying, 500 ℃ of roastings 1 hour.
(2) 10.0 gram pseudo-boehmites and 50.0 gram deionized waters are mixed, add 3.2 gram RECl x, mix, dropwise add 6.0 gram concentrated hydrochloric acids and stir, be warming up to 60 ℃, aging 2 hours, get the aged pseudo-boehmite.The product of (1) step preparation is pulverized, mixed with 15.0 gram kaolin, 15.0 gram aluminium colloidal sols, aged pseudo-boehmite and the not aged pseudo-boehmite of 10.0 grams, in 500 ℃ of roastings 2 hours.
(3) (3) step that repeats example 1～12 operates, and gets catalyst n provided by the invention, and the composition of catalyst n is listed in the table 6.
Example 15
Preparation of catalysts provided by the invention.
(1) is that 7.9 phosphoric acid solutions that weigh % mix with 30.0 gram concentration with 20.0 gram REHY and 20.0 gram USY zeolites, left standstill 6 hours that drying in 500 ℃ of roastings 1 hour, obtains phosphorous REHY and phosphorous USY respectively respectively.
(2) prepare same composition, same amount aged pseudo-boehmite by described method of (2) step of example 14.Phosphorous REHY and phosphorous USY that (1) is obtained pulverize, and mix, and mix with 20.0 gram kaolin, 20.0 gram aluminium colloidal sols, aged pseudo-boehmite and the not aged pseudo-boehmite of 15.0 grams, in 500 ℃ of roastings 3 hours again.
(3) repeat the operation that example 1～12 (3) go on foot, get catalyzer O provided by the invention, the composition of catalyzer O is listed in the table 6.
Example 16
(1) is that 4.5 ammonium dibasic phosphate solutions that weigh % mix with 20.0 gram USY zeolites and 33.7 gram concentration, left standstill 3 hours that drying in 500 ℃ of roastings 0.5 hour, obtains phosphorous USY zeolite.
(2) 22.6 gram pseudo-boehmites and 50 gram deionized waters are mixed, add 5.0 gram RECl x, mix, dropwise add 10.0 gram concentrated hydrochloric acids, stir, be warming up to 70 ℃, aging 1.5 hours, get the aged pseudo-boehmite.The product that (1) step of 12.0 grams obtains is pulverized, mixed with aged pseudo-boehmite and 10.0 gram aluminium colloidal sols, in 500 ℃ of roastings 2 hours.
(3) (3) step that repeats example 1～12 operates, and gets catalyzer M provided by the invention, and the composition of catalyzer M is listed in the table 6.
Table 6
Example number The catalyzer numbering Catalyzer is formed, heavy % Z
Zeolite Al binder Kaolin P RE 2O 3 Na 2O
13 M 32.6 37.2 22.6 0.65 5.35 1.60 1.0
14 N 45.1 25.3 24.6 0.90 3.54 0.56 1.2
15 O 52.9 17.9 23.6 1.05 3.05 1.50 2.1
16 P 48.0 41.2 0 0.92 9.46 0.42 3.8
Table 7 has been listed the weight ratio of REHY, REY, REUSY and each catalyzer middle-weight rare earths element in the example, and this weight ratio adopts x-ray fluorescence spectrometry.
Table 7
Zeolite or catalyzer La 2O 3∶CeO 2∶Pr6O 3∶Nd 2O 3(weight ratio)
REHY 23∶59∶2.6∶4.5
REY 4.7∶11.0∶2.8∶1.0
REUSY 13∶2.1 *(La 2O 3∶Nd 2O 3Weight ratio)
A or A ' 2.0∶0.5∶0.4∶0.6
B or B ' 4.7∶11.0∶2.8∶1.0
C or C ' 53.2∶13.0∶13.0∶20.8
D or D ' 9.0∶2.0∶2.0∶3.0
E or E ' 53.2∶13.0∶13.0∶20.8
F or F ' 2.0∶2.0∶0.7∶0.6
G or G ' 1.2∶0.3∶0.2∶0.4
H or H ' 4.7∶11.0∶2.8∶1.0
I 53.2∶13.0∶13.0∶20.8
J 53.2∶13.0∶13.0∶20.8
K or K ' 53.2∶13.0∶13.0∶20.8
L 53.2∶13.0∶13.0∶20.8
M 1.7∶0.4∶0.4∶0.6
N 1.1∶0.2∶0.2∶0.4
O 1.2∶0.3∶0.2∶0.4
P 53.2∶13.0∶13.0∶20.8
Example 17～32
Following example illustrates the catalytic performance of catalyzer provided by the invention.
With boiling range is that 235～335 ℃ solar oil is a reaction raw materials, on continuous micro-reactor to carrying out the light oil microactivity evaluation through catalyst A～O of 17 hours of 800 ℃ of 100% steam aging, catalyzer loading amount 5.0 grams, 460 ℃ of temperature of reaction, weight hourly space velocity 16 hours -1, the agent weight of oil is than 3.2.Evaluation result is listed in the table 8.
Comparative Examples 13～30
The catalytic performance of following Comparative Examples explanation reference catalyst.
The activity rating condition is with example 17～32, and just catalyst system therefor is reference catalyst A '～L '.Evaluation result is listed in the table 8.
Table 8
Example number The catalyzer numbering Light oil microactivity, heavy %
17 A 47
Comparative Examples 13 A’ 40
18 B 44
Comparative Examples 14 B’ 38
19 C 52
Comparative Examples 15 C’ 48
20 D 52
Comparative Examples 16 D’ 45
21 E 44
Comparative Examples 17 E’ 39
22 F 46
Comparative Examples 18 F’ 38
23 G 45
Comparative Examples 19 G’ 39
24 H 44
Comparative Examples 20 H’ 40
25 I 54
Comparative Examples 21 I’ 45
26 J 49
Comparative Examples 22 J’ 40
27 K 50
Comparative Examples 23 K’ 45
28 L 56
Comparative Examples 24 L’ 55
29 M 46
30 N 50
31 O 44
32 P 54
The result of table 7 shows that the light oil microactivity of catalyzer provided by the invention all is higher than the existing catalyzer close with its composition.
Example 33～48
Following example illustrates the catalytic performance of catalyzer provided by the invention.
With boiling range is that 227～475 ℃ decompressed wax oil (character sees Table 9) is a raw material, on the micro-reactor catalyst A～O of 4 hours of 800 ℃ of 100% steam aging is being carried out the heavy oil micro anti-evaluation continuously, catalyzer loading amount 4.0 grams, 482 ℃ of temperature of reaction, weight hourly space velocity 16 hours -1, the agent weight of oil is than 4.Table 9 has provided product yield, and diesel and gasoline ratio.Product adopts gc analysis.
Comparative Examples 25～36
The catalytic performance of following Comparative Examples explanation reference catalyst.
Evaluation method is with example 33～48, and just catalyst system therefor is 4 hours reference catalyst A ' of 800 ℃ of 100% steam aging～L ', and evaluation result is listed in the table 10.
Table 9
20 ℃ of density, gram per centimeter 3Viscosity, millimeter 2/ second 50 ℃ of 100 ℃ of bituminous matters, heavy % C 5Insolubles C 7The insoluble matter carbon residue; Heavy % total sulfur; Heavy % boiling range, the heavy % 5 10 20 30 40 50 60 70 80 90 95 of ℃ initial boiling point does 0.8652 14.58 4.37 0.60 0.026 0.04 0.42 227 274 289 322 347 373 389 401 417 431 446 458 475
Table 10
Example number The catalyzer numbering Heavy oil is little anti-
Product yield, heavy % Diesel and gasoline ratio Yield of light oil, heavy %
Gas Gasoline Solar oil Coke
33 A 10.9 51.7 23.2 1.9 0.52 74.9
Comparative Examples 25 A’ 14.1 59.6 15.2 2.6 0.30 73.7
34 B 17.6 45.4 20.4 2.4 0.44 65.8
Comparative Examples 26 B’ 21.4 50.1 15.5 4.9 0.31 65.6
35 C 12.2 48.9 19.9 1.9 0.42 68.8
Comparative Examples 27 C’ 16.9 53.8 14.3 3.0 0.27 68.1
36 D 11.2 46.3 21.9 2.2 0.47 68.2
Comparative Examples 28 D’ 14.7 53.9 16.0 3.4 0.30 69.9
37 E 11.0 44.6 22.1 1.8 0.50 66.7
Comparative Examples 29 E’ 12.4 41.3 17.2 1.8 0.42 58.5
38 F 10.0 45.4 22.0 2.2 0.48 67.4
Comparative Examples 30 F’ 14.2 53.0 14.0 3.1 0.27 67.0
39 G 10.8 47.5 22.2 1.8 0.47 69.7
Comparative Examples 31 G’ 15.4 54.6 15.2 2.7 0.28 69.8
40 H 16.6 46.5 20.8 2.0 0.45 67.3
Comparative Examples 32 H’ 17.6 43.3 17.3 2.6 0.40 60.6
41 I 11.8 48.3 20.1 1.6 0.42 68.4
Comparative Examples 33 I’ 14.0 53.0 14.8 2.8 0.28 67.8
42 J 10.3 53.2 21.2 2.2 0.40 74.4
Comparative Examples 34 J’ 11.2 52.4 17.8 2.3 0.34 70.2
43 K 12.9 55.2 20.0 2.0 0.36 75.2
Comparative Examples 35 K’ 14.9 56.0 16.8 2.3 0.30 72.8
44 L 12.8 55.3 21.8 2.0 0.40 77.1
Comparative Examples 36 L’ 14.2 54.8 19.5 2.0 0.36 74.3
45 M 10.7 47.2 22.2 1.9 0.47 69.4
46 N 10.0 54.2 21.7 2.0 0.40 72.5
47 O 10.4 45.0 22.2 2.1 0.49 67.2
48 P 12.8 55.2 18.8 2.0 0.34 74.0

Claims (12)

1. phosphorous faujusite hydrocarbon cracking catalyzer, it is characterized in that, with the catalyst weight is benchmark, this catalyzer contains faujusite 10～60 heavy %, phosphorus 0.01～1.5 heavy %, rare earth oxide 0.1～40%, weighs % in aluminum oxide al binder 10～60 heavy %, clay 0～75, described al binder is two kinds of al binders, these two kinds of al binders are respectively from pseudo-boehmite and aluminium colloidal sol, in aluminum oxide, be 0.1～10 from the weight ratio of the al binder of pseudo-boehmite and aluminium colloidal sol; Described phosphorous faujusite be with faujusite and P contained compound aqueous solution evenly after, drying, and preparing more than 0.5 hour in 450～600 ℃ of roastings.
2. according to the described catalyzer of claim 1, it is characterized in that this catalyzer contains faujusite 20～60 heavy %, al binder 10～60 heavy %, phosphorus 0.3～1.2 heavy %, rare earth oxide 0.5～10 heavy %, clay 0～65 heavy %.
3. according to the described catalyzer of claim 1, it is characterized in that the weight ratio from the binding agent of pseudo-boehmite and aluminium colloidal sol is 0.5～7.0.
4. according to each described catalyzer in the claim 1～3, it is characterized in that this catalyzer also contains the following Na of 2.5 heavy % 2O.
5. according to claim 1 or 2 described catalyzer, it is characterized in that described faujusite is selected from one or more among HY, REY, REHY, USY, REUSY, the DASY.
6. according to claim 1 or 2 described catalyzer, it is characterized in that described clay refers to kaolin.
7. claim 1 Preparation of catalysts method is characterized in that this method comprises
(1) will contain or not contain rare earth, Na 2It is even with the aqueous solution of P contained compound that O content is lower than the faujusite of 5 heavy %, left standstill 0～8 hour, and drying, in 450～600 ℃ of roastings more than 0.5 hour, must the phosphorated faujusite;
(2) phosphorous faujusite is mixed with aluminium colloidal sol and aged pseudo-boehmite slurries, behind the homogeneous in 400～600 ℃ of roastings or spraying drying, wherein in pseudo-boehmite and the aluminium colloidal sol salic weight ratio be 0.1～10;
(3) wash the product that (2) obtain.
8. according to the described method of claim 7, it is characterized in that P contained compound is selected from phosphoric acid, ammonium phosphate, Secondary ammonium phosphate or primary ammonium phosphate described in (1); The concentration of described P contained compound solution is phosphorous 0.5～2.5 heavy %, the weight ratio 0.5～5.0 of the P contained compound aqueous solution and zeolite.
9. according to the described method of claim 7, it is characterized in that roasting time described in (1) is 0.5～5 hour.
10. according to the described method of claim 7, it is characterized in that described in (2) phosphorous faujusite and aluminium colloidal sol, when aged pseudo-boehmite slurries mix, also can add clay, the add-on of clay should make argillaceous 0～75 heavy % in the final catalyzer.
11. according to the described method of claim 7, it is characterized in that containing rare earth compound in the slurries of aged pseudo-boehmite described in (2), its preparation method is: with pseudo-boehmite and water making beating, adding rare earth compound or its solution, after stirring, use quantitative hcl acidifying, wore out 0.5～3 hour in 50～80 ℃, whether rare earth adding quantity wherein can according to containing rare earth in the faujusite and content is regulated, and the content of rare earth in the slurries should guarantee that the content of rare earth in the final catalyzer reaches preset value.
12., it is characterized in that described rare earth compound is a rare earth chloride according to the described method of claim 11.
CN97120271A 1997-11-11 1997-11-11 Phosphorus-contained octahedro zeolite hydrocarbons cracking catalyst and preparation method therefor Expired - Lifetime CN1072030C (en)

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