CN1224455C - Cracking catalyst containing molecular sieve and manganese - Google Patents
Cracking catalyst containing molecular sieve and manganese Download PDFInfo
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- CN1224455C CN1224455C CN 03122863 CN03122863A CN1224455C CN 1224455 C CN1224455 C CN 1224455C CN 03122863 CN03122863 CN 03122863 CN 03122863 A CN03122863 A CN 03122863A CN 1224455 C CN1224455 C CN 1224455C
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Abstract
The present invention relates to a cracking catalyst containing a molecular sieve, a manganese additive, an RE additive and a phosphorus additive, wherein measured by P2O5, the phosphorus additive accounts for 0.2 to 10 wt%. The catalyst has high cracking activity and good coke selectivity. When used for the catalytic cracking of petroleum raw materials, the catalyst can greatly lower the olefin content in gasoline and obviously enhance the yield of light oil.
Description
Technical field
The invention relates to a kind of Cracking catalyst that contains molecular sieve, more particularly, is a kind of about containing the Cracking catalyst of molecular sieve and manganese.
Background technology
In recent years, the heaviness of catalytically cracked material and poor qualityization tendency are serious day by day, and the objectionable impurities in the raw material increases as the content of impurity such as nickel, vanadium, and the slag-mixing amount of catalytically cracked material also improves constantly.Because the existence of impurity such as nickel, vanadium can have a strong impact on the activity of Cracking catalyst, therefore, need develop the Cracking catalyst with stronger anti-metallic pollution ability.Because the heaviness of catalytically cracked material and the raising of slag-mixing amount make this raw material be difficult to cracking more, the coke that generates on the catalyst is more, and inactivation is faster, and this just requires to develop to have higher cracking activity again, and the lower Cracking catalyst of coke selectivity.
On the other hand, also having higher requirement to the total quality requirement of light oil in market, is example with gasoline, because olefin(e) centent is too high in the gasoline, the destruction of causing atmospheric ozone layer, therefore, require to reduce the olefin(e) centent in the catalytically cracked gasoline, improve the content of isoparaffin and/or aromatic hydrocarbons.
US 4,432,890 disclose the carbon monoxide-olefin polymeric of a kind of silicon oxide-containing or silica-alumina, kaolin, crystal silicon-aluminate zeolite and 1～8 weight % titanium oxide colloid and a kind of metallic addition, the amount of described metallic addition is enough under regeneration temperature, fixing vanadium in catalyst regeneration process.Described metallic addition is selected from its oxide of following metal or its salt: Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Fe, In, Tl, Bi, Te, rare earth metal.This catalyst has solved the active component in the catalyst that makes that pollution of vanadium brings, i.e. the problem that reduces of the activity of crystal aluminosilicate.
US4,750,987 disclose will contain vanadium at least the 0.1ppm hydrocarbon oil crude material be cracked into the method for light oil products.This method is included in a zone of transformation, under conversion condition, described hydrocarbon oil crude material is contacted with a kind of catalyst, this catalyst contains the metallic addition that a kind of precipitation gets on, this metallic addition can form the compound that a kind of fusing point is higher than the regeneration temperature that contains the coke catalyst with vanadium, thus fixing vanadium.This catalyst has cracking activity, also contains deposition coke and vanadium thereon after described contact; At oxygen-containing atmosphere be enough to remove under the temperature of part of coke wherein, the described catalyst that contains coke of regenerate, and the catalyst circulation after will regenerating arrives the zone of transformation that contacts with fresh feed; The amount of described metallic addition in catalyst is enough in the presence of the described oxygen-containing atmosphere and under the catalyst regeneration temperature, be fixed to the small part vfanadium compound, this metallic addition is selected from following metal, their oxide, salt and their organo-metallic compound: Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Fe, In, Tl, Bi, Te, rare earth metal.This method has suppressed the destruction of vanadium to zeolitic frameworks, thereby, can under the higher situation of catalyst vanadium content, carry out catalytic cracking to containing vanadium raw materials.
US4,485,184 disclose the catalyst that a kind of hydrocarbon oil crude material that will contain the metal that comprises vanadium of significant quantity is converted into lighter products, this catalyst contains the particle that comprises following combination: (a) host material of 10-70 weight %, this host material are selected from silica, silica-alumina and kaolin and their composition; (b) 10-40 weight % has the crystal silicon-aluminate zeolite of catalytic activity, and described zeolite is that silica alumina ratio is the faujasite of 2.5-7.0, and the granular size scope of described catalyst is the 10-200 micron, and light oil microactivity (MAT) is at least about 60 volume %; (c) trapping agent of 1-40 weight % (sacrificial trap), this trapping agent are selected from A type molecular sieve, Hydrogen or ammonium type chabasie (chabazite), column interstratified clay, the erionite (erionite) of 5A molecular sieve, modenite, Hydrogen or ammonium type (ammonium exchange), their Hydrogen or ammonium type derivative and their combination; (d) be deposited in the vanadium of the 5000-30000ppm on the described catalyst.Here, the amount of described trapping agent is enough to make, and when catalyst during by the pollution of vanadium of 5000ppm, the weight ratio of trapping agent and vanadium was greater than 10: 1, and above-mentioned all amounts are benchmark with the catalyst that is not contaminated with metals all.Above-mentioned zeolite as trapping agent can carry out ion-exchange with a metal ion species, and improve its stability or remove Na or K, and the fixing vanadium of the form by forming complex compounds with one or more metallic additions.These metallic additions are selected from one group that is made up of Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Fe, In, Tl, Bi, Te, rare earth metal.This catalyst is to have solved the problem that metal pollutant in the catalytically cracked material causes catalysqt deactivation too.
US 4,956,075 discloses a kind of catalyst cracking method, this method is at a catalytic cracking zone, in the presence of a kind of Cracking catalyst, with a kind of hydrocarbon raw material upgrading, to produce gasoline products, wherein, described Cracking catalyst contains the Mn of a kind of large pore molecular sieve and 0.1-10 weight %, and this catalyst can also contain the rare earth of 0.1-10 weight %.This method has higher gasoline selective, lower coke selectivity and C
3Following cut product selectivity.
US 5,641,395 disclose and a kind ofly have been generated as purpose to improve gasoline selective, conversion ratio, hydrogenation of olefins and/or coke, with hydrocarbon oil conversion is the method for lower molecular weight product, this method is included in the hydrogeneous riser, described hydrocarbon ils is contacted with a kind of catalyst that contains zeolite of circulation, afterwards regenerated catalyst, to remove the coke at least a portion catalyst, the combination that the improvement of this method comprises the steps: (a) retention agent weight of oil ratio is at least 3; And (b) with the catalyst weight be benchmark, at least a portion Cracking catalyst, add Mn and/or the Cr of 2400ppm at least.Adopt this method, compare with the method that adopts the catalyst that does not add Mn and Cr, the selectivity of conversion ratio and gasoline is improved, and has reduced the selectivity of coke.
In above-mentioned all prior aries, all added a kind of metallic addition in Cracking catalyst, as Mn, wherein, most Mn uses as a kind of vanadium traps, is used for suppressing the inactivation of the catalyst that brings owing to the deposition of vanadium on catalyst.US 4,956, and in 075 disclosed method, Mn that introduces in the catalyst system therefor or Mn and rare earth are used for improving selectivity, reduction coke and the C of gasoline
3Following cut product selectivity.US 5,641, and in 395 disclosed methods, the purpose of introducing Mn and/or Cr in catalyst also is to improve the selectivity of conversion ratio and gasoline, reduces the selectivity of coke.
Summary of the invention
The purpose of this invention is to provide a kind of new higher cracking activity that has, have the Cracking catalyst that contains molecular sieve and manganese that has in lower coke selectivity and the gasoline products than low olefin-content simultaneously.
Catalyst provided by the invention contains molecular sieve, manganese additive and rare earth addition, and wherein, this catalyst also contains phosphorus additive, is benchmark with the catalyst total amount, with P
2O
5Meter, the content of phosphorus additive is 0.2-10 weight %.
Catalyst provided by the invention has higher cracking activity, higher hydrothermal stability, show that the hydrocarbon oil conversion rate was higher when catalyst provided by the invention after the high-temperature water heat ageing was used for the catalytic cracking of hydrocarbon oil raw material, can obtain higher yield of light oil simultaneously.
The most outstanding advantage of catalyst provided by the invention is during with this catalyst cracking hydrocarbon oil crude material, can reduce crackate, particularly olefin content in gasoline significantly.
The another one advantage of catalyst provided by the invention is to have lower coke selectivity.
For example, catalyst provided by the invention at 800 ℃, was worn out 4 hours with 100% steam, this catalyst contains overstable gamma zeolite 32.84 weight %, and the phosphorous 1.92 weight % of the ZRP-5 zeolite with MFI structure are with P
2O
5Meter, the content of phosphorus additive is 2.06 weight %, and in MnO, the content of manganese additive is 1.96 weight %, and in rare earth oxide, the content of rare earth addition is the host material of being made up of aluminium oxide and clay of 1.97 weight % and aequum.482 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 16 hours
-1, the agent weight of oil is than being under 3 the reaction condition, is that 227-475 ℃ decompressed wax oil carries out catalytic cracking with above-mentioned catalyst provided by the invention after aging to boiling range, and conversion ratio is up to 79.7 weight %, and coke selectivity has only 0.36, C
5To boiling point is that the alkene total content is 16.17 weight % in 204 ℃ of gasoline fractions, and the content of isoparaffin and the content of aromatic hydrocarbons are respectively up to 50.23 weight % and 20.65 weight %, C
4 0/ C
4 =(C
4Alkane and C
4The volume ratio of alkene) up to 1.95.Has the ZSM-5 zeolite that same amount has the MFI structure and adopt, manganese additive is also identical with rare earth addition content, when being the reference catalyst of not phosphor-included additive, under identical reaction condition, respectively same feedstock oil is carried out catalytic cracking, its conversion ratio has only 77.1 weight %, coke selectivity is up to 0.50, and the total content of alkene is up to 22.13 weight % in the gasoline fraction, and the content of isoparaffin has only 46.58 weight %, the content of aromatic hydrocarbons has only 17.42 weight %, C
4 0/ C
4 =Have only 1.59.
The specific embodiment
According to catalyst provided by the invention, the content of phosphorus additive in the described Cracking catalyst is with P
2O
5Meter is preferably 0.5-5 weight %.The content of molecular sieve, manganese additive and rare earth addition is the content of molecular sieve, manganese additive and rare earth addition routine in the existing Cracking catalyst, in general, with the catalyst total amount is benchmark, the content of molecular sieve is 5-95 weight %, be preferably 10-70 weight %, in MnO, the content of manganese additive is 0.1-10 weight %, be preferably 0.5-5 weight %, in rare earth oxide, the content of rare earth addition is 0.5-10 weight %, is preferably 0.5-5 weight %, and to satisfy each constituent content sum of catalyst be 100 weight %.
Described molecular screening is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.These zeolites and molecular sieve are conventionally known to one of skill in the art.
Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujasite, L zeolite, Beta zeolite, omega zeolite, modenite, the ZSM-18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.
Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as zeolite (as the ZSM-5 zeolite) with MFI structure, in the zeolite with MFI structure (as phosphorous and/or rare earth ZSM-5 zeolite, the disclosed phosphorous zeolite of CN1194181A) of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more with MFI structure.
Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by the molecular sieve of one or more replacements in other element such as phosphorus, titanium, gallium, the germanium.These examples of molecular sieve comprise that the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate, titan silicate tanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metalintegrated silicoaluminophosphates (MeAPSO and ELAPSO) of metal combination, alumino-silicate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.One or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve particularly.
Under the preferable case, described molecular screening is from the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.
Described rare earth metal is selected from one or more in lanthanide series metal and the actinide metals, in preferred lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, Holmium, Er, Thulium, ytterbium, the lutetium one or more, more preferably lanthanum, cerium, lanthanum rich mischmetal or cerium-rich mischmetal metal.
Catalyst provided by the invention can also and preferably contain a kind of host material, and the kind of described host material and content are conventionally known to one of skill in the art.Described host material both can be the material with certain cracking activity, also can be the host material of inertia.Host material commonly used is selected from one or more in aluminium oxide, silica, amorphous silicon aluminium, the clay, and aluminium oxide wherein can play binding agent whole or in part.Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.Preferred clay is a kaolin.
According to an embodiment preferred of the present invention, catalyst provided by the invention contains, and is benchmark with the catalyst total amount, the molecular sieve of 10-70 weight %, and in MnO, the manganese additive of 0.5-5 weight % is with P
2O
5Meter, the phosphorus additive of 0.5-5 weight %, in rare earth oxide, the rare earth addition of 0.5-5 weight % and the host material of aequum.Described molecular screening is from the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.Described host material is selected from one or more in aluminium oxide, silica, amorphous silicon aluminium, the clay, the mixture of one or more in more preferred aluminium oxide or aluminium oxide and clay, silica, the amorphous silicon aluminium.The preferred kaolin of described clay.Described rare earth addition is selected from lanthanum, cerium, lanthanum rich mischmetal or cerium-rich mischmetal additive.
In catalyst provided by the invention, manganese additive, rare earth addition and phosphorus additive with manganese compound (as the oxide and/or the manganese salt of manganese), rare earth compound (as the oxide of rare earth metal and/or the salt of rare earth metal), phosphorus compound (as oxide, phosphate, phosphite, subphosphate and/or the acid phosphate of phosphorus) and the compound that contains two or three element in manganese, rare earth metal and the phosphorus (as phosphate, phosphite, subphosphate and/or the acid phosphate of manganese; The phosphate of rare earth, phosphite, subphosphate and/or acid phosphate; The complex compound that contains manganese, rare earth and phosphorus) form exists.Sometimes the additive of phosphorus is (as the ZRP-5 zeolite in the example) brought into by phosphorous molecular sieve own, and these non-framework of molecular sieve phosphorus also belong to the part with phosphorus additive of the present invention.Some material such as phosphorus aluminium colloidal sol can join in the catalyst, thereby brought phosphorus into to catalyst, after roasting, phosphorus aluminium colloidal sol can play the effect of host material again, particularly can play the effect of binding agent, this part phosphorus also belongs to phosphorus additive of the present invention, thereby when calculating the content of catalyst, this part phosphorus calculates in the phosphorus additive.In like manner, rare earth addition is to be brought into by the molecular sieve that itself contains rare earth sometimes, as contain rare earth y-type zeolite, contain rare earth the zeolite with MFI structure, contain the overstable gamma zeolite of rare earth etc., these rare earths also belong to the part of rare earth addition of the present invention.
Described manganese additive, rare earth addition and phosphorus additive may reside in any position that may exist of catalyst, as may reside in the inside, duct of molecular sieve, the surface of molecular sieve, may reside in the described host material, can also be present in simultaneously in the surface and described host material of inside, duct, molecular sieve of molecular sieve.
According to the requirement other to catalyst property, can also optionally contain other additive in the catalyst provided by the invention, as be used for the additive of preventing from heavy metal pollution, be used for the additive of anti-sulphur, be used to additive that reduces sulfur in gasoline content etc.For example, catalyst provided by the invention has had the performance of good anti-metallic pollution, if think further to improve the ability of its preventing from heavy metal pollution, can in catalyst, introduce among Mg, Ca, Sr, Ba, Se, Y, Ti, Zr, Hf, Nb, Ta, Zn, Tl, Bi, the Te one or more.The content of these metallic additions and introducing mode are conventionally known to one of skill in the art.
Preparation of catalysts method provided by the invention comprises manganese compound, rare earth compound and phosphorus compound is incorporated in molecular sieve and/or the host material that dry and roasting obtains product.Dry temperature is a room temperature to 400 ℃, and preferred 100-300 ℃, the temperature of roasting is 400-700 ℃, is preferably 450-650 ℃, and roasting time is 0.5-100 hour, is preferably 0.5-10 hour.The consumption of each component makes and contains molecular sieve 5-95 weight % in the final catalyst, and in MnO, the content of manganese additive is 0.1-10 weight %, and in rare earth oxide, the content of rare earth addition is 0.5-10 weight %, with P
2O
5Meter, the content of phosphorus additive is 0.2-10 weight %, contains or do not contain the host material of aequum.
Described manganese compound is selected from the various inorganic compounds of manganese and in the organic compound one or more.Described manganese compound can be soluble in water, also can be to be insoluble in water or water-fast manganese compound.The example of manganese compound comprises the oxide of manganese, the chloride of manganese, the nitrate of manganese, the phosphate of manganese, the carboxylate of manganese.Preferred manganese compound is a manganese compound soluble in water, as in the acetate of the nitrate of the chloride of manganese, manganese, manganese one or more.
Described rare earth compound is selected from the various inorganic compounds of rare earth metal and in the organic compound one or more.Described rare earth compound can be soluble in water, also can be to be insoluble in water or water-fast compound.The example of rare earth compound comprises the oxide of rare earth, the hydroxide of rare earth, the chloride of rare earth, the nitrate of rare earth, the phosphate of rare earth, the carboxylate of rare earth.In the oxide of the chloride that preferred rare earth compound is a rare earth, the hydroxide of rare earth, rare earth one or more.
Described phosphorus compound is selected from the various inorganic compounds of phosphorus and in the organic compound one or more.Described phosphorus compound can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound.The example of phosphorus compound comprises the oxide, phosphoric acid, phosphate, phosphite, hypophosphites of phosphorus, phosphorous organic compound etc.Preferred phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, manganese phosphate, aluminum phosphate, the phosphorus aluminium colloidal sol.Wherein, phosphorus aluminium colloidal sol can play the effect of phosphorus additive in catalyst, can play the effect of binding agent again.
The method that manganese compound, rare earth compound and phosphorus compound are incorporated in molecular sieve and/or the host material can adopt various existing methods.For example, when in molecular sieve, introducing manganese compound or rare earth compound, grind or do not grind after can adopting mechanical mixture, be about to water soluble or be insoluble in manganese compound or the rare earth compound and the molecular sieve mechanical mixture of water, grinding or not abrasive method then, can adopt method with manganese compound or rare earth compound aqueous solution impregnated zeolite, can adopt the method that the manganese compound aqueous solution or rare earth compound and molecular sieve are carried out ion-exchange, can adopt the manganese compound or the rare earth compound aqueous solution are mixed with molecular sieve, the precipitating reagent that adds manganese compound or rare earth compound then, manganese or rare earth are deposited to method on the molecular sieve, also the slurries of molecular sieve and manganese compound or rare earth compound aqueous solution composition can be made colloid, i.e. the method for peptization.When in molecular sieve, introducing phosphorus compound, can adopt grind or do not grind, flood after the mechanical mixture, the method for deposition and peptization.When in host material, introducing manganese compound, rare earth compound or phosphorus compound, can adopt grind after the mechanical mixture or do not grind, flood, the method for deposition and peptization, in the precursor of described host material and/or host material, introduce manganese compound, rare earth compound or phosphorus compound, in catalyst preparation process, form described host material after the precursor drying of described host material and the roasting.The precursor of described host material is selected from the material that drying and roasting can form described host material, can be selected from various hydrated aluminas (particularly boehmite), the aluminium colloidal sol one or more as the aluminium oxide precursor.The precursor of silica can be selected from one or more in Ludox, silicon gel, the waterglass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of Ludox and aluminium colloidal sol, one or more in the silica-alumina gel.
Manganese compound, rare earth compound and phosphorus compound are incorporated into molecular sieve and/or host material can carry out simultaneously, also can separately carry out.The sequencing that manganese compound, rare earth compound and phosphorus compound are introduced has no significant effect the performance of catalyst.
Add additive if catalyst also contains other, can before introducing manganese compound, rare earth compound and/or phosphorus compound, afterwards, or introduce these additives simultaneously.The method of introducing these additives is as well known to those skilled in the art.
The consumption of described each component preferably makes the molecular sieve that contains 10-70 weight % in the final catalyst, the manganese additive of 0.5-5 weight %, the rare earth addition of 0.5-5 weight %, the phosphorus additive of 0.5-5 weight % and the host material of aequum.
Catalyst provided by the invention can be used for the various petroleum distillates of catalytic cracking, to produce low-molecular-weight cut.For example, these petroleum distillates can be selected from crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, and propane is light/in heavily de-oiling, wax tailings and the coal liquefaction product one or more.Can contain beavy metal impurities such as nickel, vanadium and sulphur, nitrogen impurity in the petroleum distillate, the content of sulphur can be up to 3.0 weight %, and the content of nitrogen can be up to 2.0 weight %, and the content of metal impurities such as vanadium, nickel is up to 3000ppm.Catalyst provided by the invention is specially adapted to beavy metal impurity content such as nickel, vanadium and is not more than 3000ppm, particularly is not more than the catalytic cracking catalyst of the petroleum distillate of 200ppm, produces the gasoline that has than low olefin-content.
When using catalyst provided by the invention that petroleum distillate is carried out catalytic cracking, reaction condition is conventional catalytic cracking reaction condition, is 400-600 ℃ as reaction temperature, is preferably 450-550 ℃, and weight (hourly) space velocity (WHSV) is 10-120 hour
-1, be preferably 10-80 hour
-1, the agent weight of oil is preferably 3-15 than for 1-20.
Following example will the present invention will be further described.
Example 1
This example illustrates Catalysts and its preparation method provided by the invention.
Taking by weighing 90 gram (dry basis) lattice constants is the super steady REUSY zeolite that contains rare earth (the Zhou village catalyst plant product of 24.50 dusts, with butt weight is benchmark, sodium oxide content is 0.4 weight %, rare earth oxide content is 2 weight %, in the rare earth oxide wherein, lanthana content is 26 weight %, cerium oxide content is 45 weight %, other rare earth oxide content is 29 weight %), with 40 milliliters of ammonium phosphate solutions (containing 9.4 gram ammonium phosphate) above-mentioned overstable gamma zeolite that contains rare earth of dipping, 120 ℃ of oven dry, and then (contain 6.7 gram Mn (CH with 40 milliliters of manganese acetate aqueous solution
3COO)
24H
2O) sample after the dipping oven dry, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain catalyst C provided by the invention
1Catalyst C
1In do not contain host material.Catalyst C
1Kind and content, manganese additive and the phosphorus additive content of the kind of middle molecular sieve and content, rare earth addition are listed in the table 1.The content of each component is got by calculating in the table 1.
Each catalyst middle rare earth additive level of table 1 is in rare earth oxide, and the content of manganese additive is in MnO, and the content of phosphorus additive is with P
2O
5Meter.The content of manganese, rare earth, phosphorus additive comprises the phosphorus of bringing in any form, the summation of the content of rare earth, phosphorus additive.The kind of zeolite refers to the kind of initiation material zeolite, and zeolite content refers to deduct the clean zeolite content of wherein contained rare earth oxide and/or phosphorous oxides.When being ZRP-5 as the initiation material zeolite, because the ZRP-5 zeolite is a kind of phosphorous zeolite with MFI structure, zeolite and phosphorus can not separate, so the kind of zeolite is the ZRP-5 zeolite, and its content then refers to deduct the wherein contained oxide (P that belongs to components of additives of the present invention
2O
5) the content of ZRP-5 zeolite.And for example the initiation material zeolite is the REUSY zeolite, and the kind of zeolite is REUSY, and the content of zeolite then is the content of the contained oxide that belongs to components of additives of the present invention (rare earth oxide) the back USY zeolite of deduction.
Example 2
This example illustrates Catalysts and its preparation method provided by the invention.
(solid content is 62 weight % with 50.94 gram boehmites, the Zhou village catalyst plant is produced) mix making beating with 200 gram deionized waters, adding concentration is the aqueous hydrochloric acid solution of 36.5 volume %, the pH value of regulating slurries is 3.0, (lattice constant is 24.45 dusts to add 42 gram (dry basis) overstable gamma zeolite USY, solid content is 90 weight %, sodium oxide content is 0.4 weight %, the Zhou village catalyst plant is produced), (sodium oxide content is 0.1 weight % 2.4 gram (dry basis) has the ZSM-5 zeolite of MFI structure, silica alumina ratio is 100, the Zhou village catalyst plant is produced), stir, add 3.62 gram anhydrous lanthanum chlorides, stir, add 5.79 gram ammonium phosphate again and 179.4 gram aluminium colloidal sols (contain 21 weight %Al
2O
3, the Zhou village catalyst plant is produced), stir.At the slurries that 150 ℃ of oven dry obtain, use the 45 milliliters of dippings of the manganese chloride aqueous solution that contain tetrahydrate manganese chloride 4.14 grams then, 150 ℃ of oven dry, the solid that 600 ℃ roasting temperature obtains 1 hour obtains catalyst C provided by the invention
2Catalyst C
2Host material be aluminium oxide.C
2The content of the content of the kind of mesolite, content, manganese additive, the kind of rare earth addition and content, phosphorus additive is listed in the table 1.
Example 3
This example illustrates Catalysts and its preparation method provided by the invention.
Method according to example 2 prepares catalyst.Different is to restrain Ludox (SiO with 368.7
2Content is 10 weight %, and the Zhou village catalyst plant is produced) replace aluminium colloidal sol wherein, with 5.9 gram cerous chlorates replacements lanthanum chloride wherein, obtain catalyst C provided by the invention
3Catalyst C
3Host material be silica and aluminium oxide.C
3The content of the kind of mesolite kind and content, manganese additive, rare earth addition and content and phosphorus additive is listed in the table 1.
Example 4
This example illustrates Catalysts and its preparation method provided by the invention.
(1) with 139 gram rare earth-iron-boron (REClx, after 600 ℃ of roastings, per 100 gram REClx grams change into 68 gram mixed rare-earth oxides, in the mixed rare-earth oxide of formation, lanthana accounts for 26 weight %, cerium oxide accounts for 45 weight %, and other rare earth oxide accounts for 29 weight %, and Shanghai allosaurus Rare Earth Company is produced) and 7 kg of water, 4.4 kilogram (dry basis) overstable gamma zeolite USY (specification is with example 2) mixes, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain containing the overstable gamma zeolite of rare earth.With 4.5 kilograms of the overstable gamma zeolites that contains rare earth that obtain, mix for 8 kilograms with the aqueous solution that contains 0.25 kilogram of ammonium phosphate, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain containing the overstable gamma zeolite of rare earth and phosphorus, contain 2.58 weight %P in this zeolite
2O
5, 2.05 weight % rare earth oxides (in the rare earth oxide, lanthana content is 26 weight %, and cerium oxide content is 45 weight %, and other rare earth and oxide content are 29 weight %).
(2) with 2.54 kilograms of boehmites (specification is with embodiment 2), 3.7 (solid content is 76% to kilogram kaolin, Suzhou kaolin company produces) and 16.267 kilograms of mixing making beating of deionized water, adding concentration is the aqueous hydrochloric acid solution of 36.5 volume %, regulate slurries PH to 3, add the overstable gamma zeolite that contains rare earth and phosphorus that 2.8 kilograms (dry basis) obtains above, 0.16 the phosphorous zeolite with MFI structure of kilogram (dry basis) (produce by the Zhou village catalyst plant, the industry trade mark is ZRP-5, sodium oxide content is 0.2 weight %, in element phosphor, phosphorus content is 1 weight %, silica alumina ratio is 100), stir, add 0.157 kilogram of rare earth-iron-boron (specification is the same), 1.9 kilogram aluminium colloidal sol (specification is with embodiment 2), 0.3 kilogram of phosphorus aluminium colloidal sol (contains 9.28 weight %Al
2O
3, 30.5 weight %P
2O
5), stirring, spray-drying under 320 ℃ temperature obtains microspheres with solid.
The preparation method of described phosphorus aluminium colloidal sol is as follows:
5.8 kilograms of boehmites (are contained Al
2O
31.8 kilogram) pulled an oar 30 minutes with 4.0 kilograms of deionized waters, in slurries, add 9.6 kilograms of SPAs (85 heavy %) under stirring, be warming up to 70 ℃, under this temperature, reacted 45 minutes then, promptly make water white phosphorus aluminium colloidal sol.
(3) (contain 6.69 gram MnCl with 54 milliliters of manganese chloride aqueous solution
24H
2O) dipping 120 restrains the microspheres with solid that (dry basis) obtains above, obtains catalyst C provided by the invention
4Catalyst C
4Host material be the mixture of aluminium oxide and clay.C
4The kind of mesolite and content, the content of manganese additive, the content of the kind of rare earth addition and content and phosphorus additive is listed in the table 1.
Comparative Examples 1
This Comparative Examples illustrates reference catalyst of phosphor-included additive not and preparation method thereof.
(1) 142.7 gram rare earth-iron-borons (specification is with example 4) are mixed with 7 kilograms of deionized waters, 4.4 kilograms of (dry basis) overstable gamma zeolite USY (specification is with example 2), 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain containing the overstable gamma zeolite of rare earth.Contain 2.16 weight % rare earth oxides (in the rare earth oxide, lanthana content is 26 weight %, and cerium oxide content is 45 weight %, and other rare earth and oxide content are 29 weight %) in this zeolite.
(2) method by (2) in the example 4 and (3) prepares catalyst, different is the overstable gamma zeolite replacement overstable gamma zeolite that contains rare earth and phosphorus wherein that contains rare earth that obtains with 2.8 kilograms of these comparative example step (1), the consumption of rare earth-iron-boron is 0.159 kilogram, and kaolinic consumption is 3.99 kilograms (specification is the same).Replace the ZRP-5 zeolite with 0.16 kilogram of (dry basis) ZSM-5 zeolite (specification is with example 2), replace phosphorus aluminium colloidal sol, obtain reference catalyst CB with 0.5 kilogram of aluminium colloidal sol
1CB
1The kind of mesolite and content, the content of manganese additive, the kind and the content of rare earth addition are listed in the table 1.
Embodiment 5-6
Following example illustrates Catalysts and its preparation method provided by the invention.
Method by example 4 prepares catalyst, and different is that the consumption of phosphorus aluminium colloidal sol is respectively 0.3 kilogram and 0.56 kilogram; The consumption of rare earth-iron-boron is respectively 0.067 kilogram 0.400 kilogram; The content of tetrahydrate manganese chloride is respectively 3.35 grams and 6.69 grams in the manganese chloride aqueous solution; In the example 5, (lattice constant is 24.62 dusts to contain the y-type zeolite REHY of rare earth with 2.24 kilograms (dry basises), sodium oxide content is 0.6 weight %, mixed rare-earth oxide content is 8 weight %, and wherein, lanthana content is 26 weight % in the rare earth oxide, cerium oxide content is 45 weight %, other rare earth oxide content is 29 weight %, and the Zhou village catalyst is produced) replace the described overstable gamma zeolite that contains rare earth and phosphorus, obtain catalyst C provided by the invention
5And C
6C
5And C
6The kind of mesolite and content, the content of manganese additive, the kind of rare earth addition and content, the content of phosphorus additive is listed in the table 1.
Example 7
This example illustrates Catalysts and its preparation method provided by the invention.
Method by embodiment 4 prepares catalyst, different is before roasting and with after manganese chloride aqueous solution dipping microspheres with solid and the drying, also have one to flood described microspheres with solid with magnesium chloride brine, and in the step of 120 ℃ of oven dry, the consumption of magnesium chloride brine is 54 milliliters, contain 1.425 gram magnesium chlorides in the magnesium chloride solution, obtain catalyst C provided by the invention
7C
7The kind of mesolite and content, the content of manganese additive, the kind of rare earth addition and content, the content of phosphorus additive and magnesian content are listed in the table 1.
Table 1
| Example number | The catalyst numbering | Zeolite type and content, | Phosphorus additive content, weight % | Manganese additive content, weight % | Rare earth addition kind and content, weight % | Content of magnesia, weight % |
| 1 | C 1 | 91.48 weight %REUSY | 4.65 | 2.01 | 1.87 mishmetal | - |
| 2 | C 2 | 34.91 weight %USY+1.99 weight %ZSM-5 | 2.29 | 1.23 | 2.00 lanthanum | - |
| 3 | C 3 | 34.64 weight %USY+1.98 weight %ZSM-5 | 2.28 | 1.22 | 3.40 cerium | - |
| 4 | C 4 | 32.84 weight %USY+1.92 weight %ZRP-5 | 2.06 | 1.96 | 1.97 mishmetal | - |
| Comparative Examples 1 | CB 1 | 32.84 weight %USY+1.92 weight %ZSM-5 | - | 1.96 | 1.97 mishmetal | - |
| 5 | C 5 | 27.48 weight %REHY+2.06 weight %ZRP-5 | 2.24 | 0.98 | 3.00 mishmetal | - |
| 6 | C 6 | 31.77 weight %USY+1.88 weight %ZRP-5 | 2.93 | 1.96 | 3.92 mishmetal | - |
| 7 | C 7 | 32.68 weight %USY+1.91 weight %ZRP-5 | 2.05 | 2.01 | 1.95 mishmetal | 0.49 |
Example 8-14
Following example illustrates the catalytic performance of catalyst provided by the invention.
Catalyst C with example 1-7 preparation
1-C
7At 800 ℃, wore out 4 hours respectively with 100% steam.On heavy oil microreactor, respectively with the catalyst C after above-mentioned the wearing out
1-C
7, boiling range shown in the his-and-hers watches 2 is that 227-475 ℃ 1# feedstock oil carries out catalytic cracking.The catalyst loading amount is 4 grams, and reaction condition is as follows: reaction temperature is 482 ℃, and weight (hourly) space velocity (WHSV) is 16 hours, and agent weight of oil ratio is 3.Reaction result is listed in the table 3.
Wherein, conversion ratio=gas yield+gasoline yield+coke yield;
Yield of light oil=gasoline yield+diesel yield;
Coke selectivity=coke yield/secondary response velocity constant K;
Secondary response velocity constant K=conversion ratio/(1-conversion ratio);
Gasoline refers to that boiling range is C
5-204 ℃ cut, diesel oil refer to that boiling range is 204-330 ℃ a cut, and heavy oil refers to boiling range greater than 330 ℃ cut, and gas comprises liquefied gas and dry gas, refers to C
5Following cut.C4
0/ C4
=Weight ratio for C4 alkane in the gas and C4 alkene.
Comparative Examples 2
The performance of this Comparative Examples explanation reference catalyst.
Press the method aging catalyst of example 11, and with the catalyst after aging under identical reaction condition, identical feedstock oil is carried out catalytic cracking.Different is that catalyst system therefor is reference catalyst CB
1Reaction result is listed in the table 3.
From the result of table 3 as can be seen, with the kind of using zeolite with content is identical, the content of manganese additive and rare earth addition is also identical, but the reference catalyst of phosphor-included additive is not compared, when using catalyst cracking hydrocarbon ils provided by the invention, the hydrocarbon oil conversion rate is higher, coke selectivity is lower, olefin(e) centent reduces significantly in the gasoline fraction, and isoparaffin and arene content increase substantially, and yield of light oil obviously increases.
Table 2
| The feedstock oil numbering | 1# | 2# | 3# |
| The feedstock oil title | Vacuum gas oil (VGO) | Reduced crude | Reduced crude |
| Density (20 ℃), gram per centimeter 3 | 0.8652 | 0.9029 | 0.9036 |
| Kinematic viscosity, millimeter 2100 ℃ of/seconds | 4.37 | 15.11 | 15.3 |
| Carbon residue content, weight % | 0.04 | 3.3 | 3.34 |
| Sulfur content, weight % | 0.42 | 0.27 | 0.40 |
| Alkali nitrogen, weight % | 0.05 | 0.13 | 0.08 |
| Content of beary metal, ppm | |||
| Ni V | 0.22 0.099 | 11.6 0.3 | 3.4 3.2 |
| Flow process, ℃ initial boiling point 10% 30% 50% 70% 95% is done | 227 289 347 389 417 458 475 | 251 357 422 510 - - - | 252 343 417 495 552 - - |
Table 3
| Example number | 8 | 9 | 10 | 11 | Comparative Examples 1 | 12 | 13 | 14 |
| The catalyst numbering | C 1 | C 2 | C 3 | C 4 | CB 1 | C 5 | C 6 | C 7 |
| Conversion ratio, weight % | 85.7 | 79.0 | 79.1 | 79.7 | 77.1 | 77.8 | 78.9 | 77.4 |
| Productive rate, % by weight gas coke gasoline, diesel heavy oil light oil K coke selectivity C4 0/C 4 ＝ | 15.7 3.1 66.9 12.4 2.0 79.3 5.99 0.52 2.35 | 11.6 1.5 65.9 15.6 5.4 81.5 3.76 0.40 1.64 | 11.7 1.5 65.9 15.6 5.3 81.5 3.78 0.40 1.89 | 11.5 1.4 66.8 15.8 5.0 82.6 3.93 0.36 1.95 | 11.8 1.7 63.6 15.0 7.9 78.6 3.37 0.50 1.59 | 11.2 1.4 65.2 16.4 5.8 81.6 3.50 0.40 1.78 | 11.2 1.4 66.3 15.6 5.5 81.9 3.74 0.37 1.84 | 11.0 1.4 65.0 16.8 5.8 81.8 3.42 0.41 1.72 |
| Gasoline is formed, weight % N-alkanes isomeric alkane cycloalkanes alkene aromatic hydrocarbons | 5.04 50.25 7.51 12.92 24.28 | 4.63 49.34 8.30 18.36 19.37 | 4.26 50.75 8.62 16.75 19.62 | 4.42 50.23 8.53 16.17 20.65 | 4.51 46.58 9.36 22.13 17.42 | 4.37 48.62 8.46 17.24 21.31 | 4.54 48.56 8.69 16.88 21.33 | 4.58 49.46 8.72 17.87 19.37 |
Example 15-16
Following example illustrates the catalytic performance of catalyst provided by the invention.
Method by example 11 is carried out catalytic cracking to identical raw material, and different is, the reaction condition difference, and reaction condition and reaction result are listed in the table 4.
Table 4
| Example number | 15 | 16 |
| The catalyst numbering | C 4 | C 4 |
| Reaction temperature, ℃ | 502 | 492 |
| Weight (hourly) space velocity (WHSV), hour -1 | 25 | 16 |
| Agent weight of oil ratio | 3 | 4 |
| Conversion ratio, weight % | 77.5 | 83.3 |
| Product yield, weight % gas coke gasoline, diesel heavy oil light oil | 11.0 1.3 65.2 16.8 5.7 82.0 | 13.2 1.8 68.3 13.5 3.2 81.8 |
| Gasoline is formed, weight % N-alkanes isomeric alkane cycloalkanes alkene aromatic hydrocarbons | 4.43 46.53 8.22 21.18 19.64 | 4.52 51.56 8.72 14.23 20.97 |
Example 17-19
Following example illustrates the catalytic performance of catalyst provided by the invention.
Method by example 11 is carried out catalytic cracking to hydrocarbon ils, and different is that raw materials used oil is respectively 2# shown in the table 2 and 3# feedstock oil, and catalyst system therefor, reaction condition, feedstock oil and reaction result are listed in the table 5.
Table 5
| Example number | 17 | 18 | 19 |
| The catalyst numbering | C 4 | C 6 | C 7 |
| Feedstock oil | 2# | 3# | 3# |
| Reaction temperature, ℃ | 492 | 502 | 512 |
| Weight (hourly) space velocity (WHSV), hour -1 | 16 | 16 | 16 |
| Agent weight of oil ratio | 3 | 3 | 3 |
| Conversion ratio, weight % | 78 | 75.8 | 75.4 |
| Product yield, weight % dry gas+liquefied gas coke gasoline, diesel heavy oil light oil | 11.0 2.5 64.5 15.5 6.5 80 | 10.6 2.5 62.7 15.8 8.4 78.5 | 10.5 2.1 62.8 17.2 7.4 80.0 |
| Gasoline is formed, weight % n-alkane isoparaffin cycloalkane alkene aromatic hydrocarbons | 4.25 40.56 8.58 25.13 21.48 | 4.54 39.27 8.14 24.69 23.36 | 4.23 41.54 8.16 22.87 23.20 |
Claims (11)
1. Cracking catalyst that contains molecular sieve, manganese and rare earth, this catalyst contains molecular sieve, manganese additive, rare earth addition and phosphorus additive, with the catalyst total amount is benchmark, the content of molecular sieve is 5-95 weight %, in MnO, the content of manganese additive is 0.1-10 weight %, in rare earth oxide, the content of rare earth addition is 0.5-10 weight %, with P
2O
5Meter, the content of phosphorus additive is 0.2-10 weight %, and to satisfy each constituent content sum of catalyst be 100 weight %.
2. catalyst according to claim 1 is characterized in that, the content of described phosphorus additive is 0.5-5 weight %.
3. catalyst according to claim 1 is characterized in that, the content of molecular sieve is 10-70 weight %, and the content of manganese additive is 0.5-5 weight %, and the content of rare earth addition is 0.5-5 weight %.
4. catalyst according to claim 1 is characterized in that, described molecular screening one or more in macropore or mesopore zeolite.
5. catalyst according to claim 4 is characterized in that, described molecular screening from y-type zeolite, Beta zeolite, have in the zeolite of MFI structure one or more.
6. catalyst according to claim 1 is characterized in that, described rare earth addition is selected from lanthanum, cerium, lanthanum rich mischmetal or cerium-rich mischmetal additive.
7. catalyst according to claim 1 is characterized in that this catalyst also contains a kind of host material.
8. catalyst according to claim 7 is characterized in that, described host material is selected from one or more the mixture in aluminium oxide or aluminium oxide and clay, silica, the amorphous aluminum silicide.
9. catalyst according to claim 1 is characterized in that this catalyst contains, and is benchmark with the catalyst total amount, the molecular sieve of 10-70 weight %, in MnO, the manganese additive of 0.5-5 weight %, in rare earth oxide, the rare earth addition of 0.5-5 weight % is with P
2O
5Meter, the phosphorus additive of 0.5-5 weight % and the host material of aequum; Described molecular screening from y-type zeolite, Beta zeolite, have in the zeolite of MFI structure one or more; Described host material is selected from one or more in aluminium oxide, silica, amorphous aluminum silicide, the clay.
10. catalyst according to claim 9 is characterized in that, described host material is selected from one or more the mixture in aluminium oxide or aluminium oxide and clay, silica, the amorphous aluminum silicide.
11., it is characterized in that described clay refers to kaolin according to claim 9 or 10 described catalyst.
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| CN100391610C (en) * | 2005-08-15 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic cracking fluid bed catalyst containing molecular sieve |
| US9480975B2 (en) | 2005-08-15 | 2016-11-01 | China Petroleum & Chemical Corporation | Catalyst for catalytic cracking in a fluidized bed |
| CN101733140B (en) * | 2008-11-18 | 2012-01-11 | 中国石油天然气股份有限公司 | Preparation method of shape-selective molecular sieve composition |
| CN101822995B (en) * | 2009-03-02 | 2012-10-10 | 中国石油化工股份有限公司 | Heavy oil cracking catalyst and preparation method thereof |
| CN101822998B (en) * | 2009-03-02 | 2012-11-14 | 中国石油化工股份有限公司 | Heavy oil cracking catalyst and preparation method thereof |
| CN101992116B (en) * | 2009-08-10 | 2014-05-28 | 北京石油化工学院 | MnMe/molecular sieve series catalysts and preparation and application thereof |
| CN114425453B (en) * | 2020-09-25 | 2024-01-09 | 中国石油化工股份有限公司 | Multifunctional catalytic cracking metal trapping agent and preparation method thereof |
| CN114425400B (en) * | 2020-09-25 | 2023-12-12 | 中国石油化工股份有限公司 | Wear-resistant catalytic cracking catalyst and preparation method and application thereof |
| CN114425376B (en) * | 2020-09-27 | 2024-03-12 | 中国石油化工股份有限公司 | Hydrocarbon conversion catalyst containing MFI zeolite and its preparation method |
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