CN1267190C - Cracking catalyst containing molecular sieve and manganese - Google Patents
Cracking catalyst containing molecular sieve and manganese Download PDFInfo
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- CN1267190C CN1267190C CN 03122865 CN03122865A CN1267190C CN 1267190 C CN1267190 C CN 1267190C CN 03122865 CN03122865 CN 03122865 CN 03122865 A CN03122865 A CN 03122865A CN 1267190 C CN1267190 C CN 1267190C
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Abstract
The present invention relates to a cracking catalyst containing a molecular sieve, a manganese additive and a phosphorus additive; on the basis of the total amount of the catalyst, measured by P2O5, the content of the phosphorus additive is from 0.2 to 10 wt%. The catalyst has the advantages of high cracking activity and good coke selectivity. When used for catalytically cracking petroleum fractions, the catalyst can greatly reduce lower olefin content in gasoline.
Description
Technical field
The invention relates to a kind of Cracking catalyst that contains molecular sieve, more particularly, is the Cracking catalyst that contains molecular sieve and manganese about a kind of.
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 lower coke selectivity simultaneously, and have the Cracking catalyst that contains molecular sieve and manganese in the gasoline products than low olefin-content.
Catalyst provided by the invention contains molecular sieve and manganese additive, 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, and higher hydrothermal stability shows that conversion ratio 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.
The most outstanding advantage of catalyst provided by the invention is during with this catalyst cracking hydrocarbon oil crude material, in the cracked product, particularly have lower olefin(e) centent and higher isoparaffin, arene content in the gasoline products, adapted to the requirement of olefin(e) centent in the market minimizing cracking gasoline.
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 34.99 weight %, and the phosphorous 1.93 weight % of the ZRP-5 zeolite with MFI structure are with P
2O
5Meter, the content of phosphorus additive is 2.33 weight %, in MnO, the content of manganese additive is the host material of being made up of aluminium oxide and clay of 0.99 weight % and surplus.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, conversion ratio is up to 79.2 weight %, C
5To boiling point is that the alkene total content is 17.88 weight % in 204 ℃ of gasoline fractions.C
4 0/ C
4=(C
4Alkane and C
4The volume ratio of alkene) up to 1.79, coke selectivity has only 0.39.Has the ZSM-5 zeolite that same amount has the MFI structure and adopt, manganese additive content is identical, just the reference catalyst and the zeolite type of phosphor-included additive are all not identical with content, phosphorus additive content is identical, does not just contain the reference catalyst of manganese additive, under identical reaction condition, respectively same feedstock oil is carried out catalytic cracking, its conversion ratio has only 75.1 weight % and 75.9 weight % respectively, and the total content of alkene is respectively up to 23.0 weight % and 21.9 weight %, C in the gasoline fraction
4 0/ C
4 =Have only 1.42 and 1.52 respectively, coke selectivity is then respectively up to 0.50 and 0.48.
The specific embodiment
According to catalyst provided by the invention, with P
2O
5Meter, the content of phosphorus additive is preferably 0.5-5 weight %.In described Cracking catalyst, the content of molecular sieve and manganese additive is the content of molecular sieve and manganese additive routine in the existing Cracking catalyst, in general, with the catalyst total amount is benchmark, in MnO, the content of manganese additive is 0.1-10 weight %, is preferably 0.5-5 weight %; The content of molecular sieve is 5-95 weight %, is preferably 10-70 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 titanosilicate), 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.
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 % 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.
In catalyst provided by the invention, manganese additive and phosphorus additive exist with manganese compound (as oxide, the manganese salt of manganese), phosphorus compound (as oxide, phosphate, phosphite, subphosphate and/or the acid phosphate of phosphorus) and/or the form that contains the compound (as phosphate, phosphite, subphosphate, the acid phosphate of manganese) of manganese and phosphorus.Some phosphorus additive 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 of 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.The situation of manganese additive is the same with the situation of phosphorus additive.
Described manganese additive 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 and phosphorus compound is incorporated in molecular sieve and/or the host material, the product dry and roasting obtains, dry temperature is a room temperature to 400 ℃, preferred 100-300 ℃, the temperature of roasting is 400-700 ℃, be preferably 450-650 ℃, 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, manganese additive is 0.1-10 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 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 and phosphorus compound are incorporated in molecular sieve and/or the host material can adopt various existing methods.When for example in molecular sieve, introducing manganese compound, grind or do not grind after can adopting mechanical mixture, be about to water soluble or be insoluble in the manganese compound and the molecular sieve mechanical mixture of water, grinding or not abrasive method then, can adopt method with manganese compound aqueous solution impregnated zeolite, can adopt the method that the manganese compound aqueous solution and molecular sieve are carried out ion-exchange, can adopt the manganese compound aqueous solution is mixed with molecular sieve, the precipitating reagent that adds manganese compound then, with the method for manganese deposition to the molecular sieve, also the slurries of molecular sieve and manganese 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 and phosphorus compound, can adopt grind or do not grind, flood after the mechanical mixture, the method for deposition and peptization, in the precursor of described host material and/or host material, introduce manganese compound and 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.
With manganese compound with phosphorus compound is incorporated into molecular sieve and/or host material can carry out simultaneously, also can separately carry out, the sequencing that manganese compound and phosphorus compound are introduced has no significant effect the performance of catalyst.
If catalyst also contains other additive, can before introducing manganese 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 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.
(solid content is 90 weight % to take by weighing lattice constant and be the overstable gamma zeolite USY of 24.45 dusts, sodium oxide content is 0.4 weight %, the Zhou village catalyst plant is produced) 100 grams, flood above-mentioned overstable gamma zeolite with 40 milliliters of ammonium phosphate solutions (containing 9.3 gram ammonium phosphate), 120 ℃ of oven dry, and then (contain 6.65 gram Mn (CH with 40 milliliters of manganese acetate aqueous solution
3COO)
24H
2O) dipping, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain catalyst C provided by the invention
1Catalyst C
1In do not contain host material.The content of molecular sieve, manganese additive and phosphorus additive is listed in table 1 in the catalyst.The content of each component is got by calculating.The content of manganese additive is in MnO in the table 1, and the content of phosphorus additive is with P
2O
5Meter, phosphorus additive and manganese additive content comprise non-framework of molecular sieve phosphorus and the manganese of bringing in any form, zeolite content refers to deduct wherein contained MnO and P
2O
5The content of back zeolite.
Example 2
This example illustrates Catalysts and its preparation method provided by the invention.
With 42 gram (dry basis) overstable gamma zeolites (specification is with example 1), 2.4 the phosphorous zeolite with MFI structure of gram (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), 341 gram aluminium colloidal sol (salic 21 weight %, the Zhou village catalyst plant is produced), 5.79 gram ammonium phosphate and 68 gram deionized waters mix, stirring down, 20 milliliters of manganese acetate aqueous solution of adding (contain 4.14 gram Mn (CH
3COO)
24H
2O), make the slurries that solid content is 25 weight %, the slurries that obtain 150 ℃ of oven dry, the solid that obtains at 450 ℃ roasting temperature is 2 hours then, obtains catalyst C provided by the invention
2Catalyst C
2Host material be aluminium oxide.C
2The content of the kind of mesolite and content and manganese additive and phosphorus additive is listed in the table 1.
Example 3
This example illustrates Catalysts and its preparation method provided by the invention.
18 grams (dry basis) are contained the y-type zeolite REY of rare earth, and (sodium oxide content is 0.5 weight %, mixed rare-earth oxide content is 17 weight %, wherein, lanthana content in the rare earth oxide is 26 weight %, cerium oxide content is 45 weight %, other rare earth oxide content is 29 weight %, the Zhou village catalyst is produced), 2.4 gram (dry basis) silica alumina ratio is that (sodium oxide content is 0.1 weight % for 100 the ZSM-5 zeolite with MFI structure, the Zhou village catalyst plant is produced), 107.7 (solid content is 61% to the gram boehmite, the Zhou village catalyst plant is produced), 300 gram Ludox (solid content is 10 weight %, and the Zhou village catalyst plant is produced), 4.14 gram Mn (CH
3COO)
24H
2O and 37 gram deionized waters mix.Under agitation, adding concentration is the aqueous hydrochloric acid solution of 36.5 volume %, and the pH value of regulating slurries is 3.Continue to stir, make slurries form uniform colloid, continue to stir down, add 10 milliliters of ammonium phosphate solutions (phosphoric acid ammonium 5.66 grams), stir, obtain the colloid that solid content is 25 weight %, at 180 ℃ of these colloids of oven dry, the solid that obtains at 550 ℃ roasting temperature is 1.5 hours then, obtains catalyst C provided by the invention
3Catalyst C
3Host material be silica and aluminium oxide.C
3The content of mesolite kind and content and manganese additive, phosphorus additive is listed in the table 1.
Example 4
This example illustrates Catalysts and its preparation method provided by the invention.
With 2 kilograms of boehmites (specification is with example 3), 4.0 (solid content is 80 content % to kilogram kaolin, Suzhou kaolin company produces) and 16 kilograms of deionized waters mix, the hydrochloric acid solution that under agitation adds 36.5 volume %, regulate the PH to 3 of slurries, add 3.1 kilograms of (dry basis) overstable gamma zeolites (specification is with example 1) and 0.175 kilogram of ZRP-5 zeolite (specification is with example 2), back adding 4 kilograms of aluminium colloidal sols (specification is with example 2) stir, 0.365 kilogram phosphorus aluminium colloidal sol (aluminium oxide that contains 9.28 weight %, the P of 30.5 weight %
2O
5), stirring, spray-drying under 350 ℃ temperature gets microspheres with solid.With 120 gram (dry basis) microspheres with solid earlier with 45 milliliters of ammonium phosphate solutions (containing 2.63 gram ammonium phosphate) dipping, 120 ℃ of oven dry, and then (contain 4.18 and restrain MnCl with 45 milliliters of manganese chloride aqueous solution
24H
2O) dipping, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain catalyst C provided by the invention
4Catalyst C
4Host material be aluminium oxide and kaolin.C
4The content of the kind of mesolite and content, phosphorus additive, the content of manganese additive are listed in table 1.
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 phosphorated aluminiferous collosol.
Comparative Examples 1
This Comparative Examples illustrates the not Catalysts and its preparation method of phosphor-included additive.
Method by example 4 prepares catalyst, different is with 171 gram silica alumina ratios is that 100 ZSM-5 zeolite (specification is with example 3) replaces ZRP-5, replace described phosphorus aluminium colloidal sol with 0.782 kilogram of aluminium colloidal sol,, obtain reference catalyst CB without ammonium phosphate solution dipping microspheres with solid
1CB
1The content of mesolite kind and content, manganese additive is listed in the table 1.
Comparative Examples 2
The explanation of this Comparative Examples does not contain the Catalysts and its preparation method of manganese additive.
Method by example 4 prepares catalyst, different is, the USY consumption is 3.068 kilograms (butts), the kaolin consumption is 4.042 kilograms, ZRP-5 is 0.173 kilogram (butt), only floods microspheres with solid with 45 milliliters of ammonium phosphate solutions (containing 2.58 gram ammonium phosphate), after the drying directly 600 ℃ of roastings 2 hours, the step of manganese chloride solution dipping of no use obtains reference catalyst CB
2CB
2The content of mesolite kind and content and phosphorus additive is listed in the table 1.
Example 5-7
Following example illustrates Catalysts and its preparation method provided by the invention.
Method by example 4 prepares catalyst, and different is that the kaolin consumption is respectively 3.2 kilograms (dry basises), 4 kilograms (dry basis) and 3.45 kilograms (dry basis); During dipping in the ammonium phosphate solution content of ammonium phosphate be respectively 7.6 grams, 2.55 grams and 5.09 restrain; The content of tetrahydrate manganese chloride is respectively 5.1 grams in the manganese chloride aqueous solution, 1.7 gram and 6.8 grams, (lattice constant is 24.62 dusts to contain the y-type zeolite REHY of rare earth with 2.48 kilograms (dry basises) in the example 6 and 7, sodium oxide content is 0.6 weight %, mixed rare-earth oxide content is 8 weight %, 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 %, the Zhou village catalyst is produced) and 2.66 kilograms of (dry basis) super-stable Y zeolite containing rare-earth elements REUSY (lattice constant is 24.49 dusts, sodium oxide content is 0.4 weight %, mixed rare-earth oxide content is 2 weight %, and wherein, the lanthana content of rare earth oxide is 26 weight %, cerium oxide content is 45 weight %, other rare earth oxide content is 29 weight %, and the Zhou village catalyst is produced) replace overstable gamma zeolite, obtain catalyst C provided by the invention
5, C
6And C
7C
5, C
6And C
7The content of mesolite kind and content, manganese additive and phosphorus additive is listed in the table 1.
Example 8
Following example illustrates Catalysts and its preparation method provided by the invention.
Method by example 4 prepares catalyst, different is before roasting, after manganese chloride aqueous solution dipping and drying, also have 45 milliliters of magnesium nitrate aqueous solutions of a usefulness (containing 2.32 gram anhydrous nitric acid magnesium) described microspheres with solid of dipping and, obtain catalyst C provided by the invention in the step of 120 ℃ of oven dry
8C
8The content of mesolite kind and content, manganese additive, phosphorus additive and the content of magnesium (in oxide) are listed in the table 1.
Example 9-16
Following example illustrates the catalytic performance of catalyst provided by the invention.
The catalyst C that example 1-8 is obtained
1-C
8At 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
8, boiling range shown in the his-and-hers watches 2 is that 227-475 ℃ decompressed wax 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
-1, 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 3-4
The performance of following example explanation reference catalyst.
Press the method aging catalyst of example 12, and under identical condition the identical raw material of catalytic cracking.Different is to use reference catalyst CB respectively
1And CB
2Replace catalyst C
4Reaction result is listed in the table 3.
From the result of table 3 as can be seen, identical with the kind and the content of zeolite, phosphor-included additive or do not contain the reference catalyst CB of manganese additive not
1And CB
2Compare, the catalyst provided by the invention that contains phosphorus additive and manganese additive simultaneously has higher cracking performance, lower coke selectivity, higher yield of light oil, and olefin(e) centent reduces significantly in the gasoline fraction, the content of isoparaffin increases substantially, and arene content also is significantly improved.
Table 1
| Example number | The catalyst numbering | Zeolite type and content | Phosphorus additive content, weight % | Manganese additive content, weight % | Content of magnesia, weight % |
| 1 | C 1 | 93.40 weight %USY | 4.60 | 2.00 | - |
| 2 | C 2 | 35.01 weight %USY+1.95 weight %ZRP-5 | 2.35 | 1.00 | - |
| 3 | C 3 | 15.00 weight %REY+1.95 weight %ZSM-5 | 2.30 | 1.00 | - |
| 4 | C 4 | 34.99 weight %USY+1.93 weight %ZRP-5 | 2.33 | 0.99 | - |
| Comparative Examples 1 | CB 1 | 34.99 weight %USY+1.93 weight %ZSM-5 | - | 0.99 | - |
| Comparative Examples 2 | CB 2 | 34.99 weight %USY+1.93 weight %ZRP-5 | 2.33 | - | - |
| 5 | C 5 | 33.73 weight %USY+1.86 weight %ZRP-5 | 4.11 | 1.44 | - |
| 6 | C 6 | 27.23 weight %REHY+1.88 weight %ZRP-5 | 2.23 | 0.49 | - |
| 7 | C 7 | 29.72 weight %REUSY+1.91 weight %ZRP-5 | 3.21 | 1.93 | - |
| 8 | C 8 | 34.81 weight %USY+1.92 weight %ZRP-5 | 2.32 | 0.98 | 0.51 |
Table 2
| The feedstock oil numbering | 1# | 2# | 3# |
| The feedstock oil title | Decompressed wax oil | 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 | 15.30 |
| 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 | 9 | 10 | 11 | 12 | Contrast 1 | Contrast 2 | 13 | 14 | 15 | 16 |
| The catalyst numbering | C 1 | C 2 | C 3 | C 4 | CB 1 | CB 2 | C 5 | C 6 | C 7 | C 8 |
| Conversion ratio, weight % | 84.3 | 76.9 | 78.7 | 79.2 | 75.1 | 75.9 | 77.7 | 77.0 | 79.0 | 77.2 |
| Productive rate, % by weight gas coke gasoline, diesel heavy oil light oil K coke selectivity | 14.0 2.8 67.5 12.1 3.6 79.2 5.37 0.52 | 12.5 1.5 62.9 17.9 5.2 80.8 3.33 0.45 | 12.6 1.7 64.4 14.9 6.4 79.3 3.69 0.46 | 11.9 1.5 65.8 15.3 5.5 81.1 3.81 0.39 | 11.6 1.5 62.0 15.6 9.3 77.6 3.02 0.50 | 11.5 1.5 62.9 15.5 8.6 78.4 3.15 0.48 | 11.5 1.4 64.7 15.4 6.9 80.1 3.48 0.40 | 12.4 1.4 63.2 16.9 6.1 80.1 3.35 0.42 | 12.1 1.5 65.4 14.4 6.6 79.7 3.76 0.40 | 12.7 1.5 63.0 17.1 5.7 80.1 3.39 0.44 |
| C 4 0/C 4 ＝ | 2.01 | 1.55 | 1.83 | 1.79 | 1.42 | 1.52 | 1.66 | 1.58 | 1.88 | 1.58 |
| Gasoline is formed, weight % N-alkanes isomeric alkane cycloalkanes alkene aromatic hydrocarbons | 5.02 53.12 7.56 14.30 20.00 | 4.67 48.69 8.55 20.07 18.02 | 4.91 51.1 8.03 17.09 18.87 | 4.52 49.18 8.97 17.88 19.45 | 4.53 45.67 9.57 23.0 17.23 | 4.32 46.15 9.89 21.9 17.74 | 4.43 49.43 9.55 18.3 18.29 | 4.56 49.58 8.61 18.39 18.86 | 4.27 50.10 9.52 16.77 19.34 | 4.35 48.87 8.8 19.89 18.09 |
Example 17-18
Following example illustrates the catalytic performance of catalyst provided by the invention.
Method by example 12 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 | 17 | 18 |
| 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 % | 74.5 | 83.5 |
| Product yield, weight % gas coke gasoline, diesel heavy oil light oil | 10.5 1.2 62.8 17.3 8.2 80.1 | 14.4 2.0 67.1 13.5 3.0 80.6 |
| Gasoline is formed, weight % N-alkanes isomeric alkane cycloalkanes alkene aromatic hydrocarbons | 4.12 48.38 8.29 21.56 17.65 | 4.62 52.35 8.75 14.30 19.98 |
Example 19-20
Following example illustrates the catalytic performance of catalyst provided by the invention.
Method by example 12 is carried out catalytic cracking to feedstock oil, and different is that raw materials used oil is respectively 2# shown in the table 2 and 3# feedstock oil.Catalyst system therefor, reaction condition and reaction result are listed in the table 5.
Table 5
| Example number | 19 | 20 | 21 |
| The catalyst numbering | C 4 | C 4 | C 8 |
| 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 % | 75.6 | 74.3 | 74.7 |
| Product yield, weight % gas coke gasoline, diesel heavy oil light oil | 10.9 2.6 62.1 16.0 8.4 81.1 | 10.4 2.5 61.4 15.9 9.8 81.1 | 10.5 2.3 61.9 16.4 8.9 78.3 |
| Gasoline is formed, weight % n-alkane isoparaffin cycloalkane alkene aromatic hydrocarbons | 4.34 40.25 9.67 25.48 20.26 | 4.56 38.26 9.05 26.79 21.34 | 4.23 41.17 9.13 25.32 20.15 |
Claims (13)
1. Cracking catalyst that contains molecular sieve and manganese, this catalyst is made up of molecular sieve, manganese additive and phosphorus additive basically, with the catalyst total amount is benchmark, the content of molecular sieve is 5-95 weight %, in oxide, the content of manganese additive is 0.1-10 weight %, and 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 %.
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, it is characterized in that, 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.
6. catalyst according to claim 1 is characterized in that this catalyst also contains a kind of host material.
7. catalyst according to claim 6 is characterized in that described host material is selected from one or more in aluminium oxide, silica, amorphous aluminum silicide, the clay.
8. catalyst according to claim 7 is characterized in that described clay refers to kaolin.
9. Cracking catalyst that contains molecular sieve and manganese, this catalyst contains molecular sieve and manganese additive, it is characterized in that, this catalyst also contains phosphorus additive, this catalyst by comprise with manganese compound and phosphorus compound be incorporated in the molecular sieve, the method preparation of dry and roasting, the consumption of each component makes and contains molecular sieve 5-95 weight % in the final catalyst, in MnO, manganese additive is 0.1-10 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 %, and dry temperature is a room temperature to 400 ℃, and the temperature of roasting is 400-700 ℃, and roasting time is 0.5-100 hour.
10. catalyst according to claim 9, it is characterized in that, also contain host material in the described catalyst, this catalyst by comprise with manganese compound and phosphorus compound be incorporated in molecular sieve and the matrix, the method preparation of dry and roasting, the consumption of each component makes and contains molecular sieve 5-95 weight % in the final catalyst, in MnO, manganese additive is 0.1-10 weight %, with P
2O
5Meter, the content of phosphorus additive is 0.2-10 weight %, and host material is an aequum, and dry temperature is a room temperature to 400 ℃, and the temperature of roasting is 400-700 ℃, roasting time is 0.5-100 hour.
According to claim 9 or 10 described catalyst, it is characterized in that 11, the temperature of described drying is 100-300 ℃, the temperature of roasting is 450-650 ℃, and roasting time is 0.5-10 hour.
12, catalyst according to claim 10 is characterized in that, described host material is selected from one or more in aluminium oxide, silica, amorphous aluminum silicide, the clay.
13. catalyst according to claim 12 is characterized in that, described clay refers to kaolin.
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