CN101822998A - Heavy oil cracking catalyst and preparation method thereof - Google Patents
Heavy oil cracking catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst and a preparation method thereof, in particular to a heavy oil cracking catalyst and a preparation method thereof. The catalyst contains zeolite and a composite, wherein the composite contains rectorite, heat-resistant inorganic oxide and auxiliary agent; by taking the total weight of the composite as the reference, the content of the rectorite is 45-94.9 wt%, and the content of the heat-resistant inorganic oxide is 5-50 wt%, the content of the auxiliary agent is 0.1-20 wt% by elements, and the auxiliary agent is Mn compound, or one or mixture of the Mn compound, the P compound and the Ce compound. The catalyst has excellent anti-metal performance when being used in heavy oil cracking reaction, and can increase the weight ratio of liquefied gas, gasoline and diesel fuel in the product.
Description
Technical field
The invention relates to a kind of Catalysts and its preparation method, particularly about a kind of catalyst for cracking heavy oil and preparation method thereof.
Background technology
The change weight of feedstock oil and refinery require to improve the ability of Cracking catalyst cracked fuel oil to the pursuit of economic benefit.The channel diameter of y-type zeolite is 0.75nm in the Cracking catalyst, and the middle small molecule hydrocarbon in the feedstock oil can enter zeolite endoporus generation cracking reaction, and big molecule hydrocarbon is difficult to enter the zeolite endoporus.In order to improve cracking ability to heavy end, usually the carrier of Cracking catalyst has macropore and the certain acidity that the big molecule of heavy oil can enter, big molecule in the heavy oil is cracked into earlier medium sized molecule in the macropore of carrier, medium sized then molecule enters acid stronger zeolite cavity again, further is cracked into less molecule.
CN1211608A discloses a kind of laminar column clay microphere cracking catalyst for heavy oil that is used for voluminous gasoline and diesel oil, and this agent has following composition: the chemical composition of the laminated clay column of 20-90 weight %, 10-40 weight % is mainly the y-type zeolite of the binding agent of aluminium oxide, 0-40 weight % and kaolin group's clay of 0-70 weight %.
CN1175086C discloses a kind of Cracking catalyst that contains lamellar clay, this catalyst is prepared by following method: swellable clay, adjuvant component, boehmite and water are mixed making beating 0.1-10 hour, obtain a kind of slurries, under 50-85 ℃ temperature, wore out slurries 0.1-10 hour, drying and moulding, washing are worn out then, final drying and roasting, described adjuvant component be selected from the hydroxy polymer of silicon, aluminium, zirconium or titanium one or more or contain in one or more the material in the described hydroxy polymer one or more.
CN10121087A discloses a kind of catalyst for cracking heavy oil, this catalyst contains zeolite and clay, wherein, described clay contains a kind of tired soil that takes off that contains auxiliary agent at least, gross weight with clay is a benchmark, the tired content that takes off soil that contains adjuvant component is 5-100 weight %, with the tired weight of taking off soil that contains adjuvant component is benchmark, the described tired tired soil that takes off that contains 45-94.9 weight % in the soil that takes off that contains adjuvant component, in the binder component of oxide 5-50 weight %, in the P that is selected from of element 0.1-20 weight %, Mg, RE, Ti, the adjuvant component of one or more among B and the Zr.
The anti-metallicity of above catalyst for cracking heavy oil is bad, and the percentage of the gross weight of liquefied gas, gasoline and diesel oil in product is not high.
Summary of the invention
The objective of the invention is to strengthen the anti-metallicity of catalyst for cracking heavy oil, provide a kind of and have outstanding anti-metallicity, and can improve the catalyst of the weight ratio of liquefied gas in the product, gasoline and diesel oil.
The invention provides a kind of catalyst, this catalyst contains zeolite and a kind of composition, wherein, said composition contains rectorite, heat-resistant inorganic oxide and auxiliary agent, gross weight with said composition is a benchmark, the content of described rectorite is 45-94.9 weight %, the content of heat-resistant inorganic oxide is 5-50 weight %, content in the element auxiliary agent is 0.1-20 weight %, described auxiliary agent is the compound of Mn, perhaps is one or both the mixture in the compound of the compound of the compound of Mn and P and Ce.
The invention provides a kind of Preparation of catalysts method, this method comprises:
With rectorite, heat-resistant inorganic oxide and/or its precursor and water mix making beating, and under 60 ℃-80 ℃, stirred 30-120 minute, add auxiliary agent, stir more than 30 minutes, make first slurries, described rectorite, heat-resistant inorganic oxide and/or its precursor, it is 10-60 weight % that the consumption of auxiliary agent and water makes the solid content of first slurries that obtain, and rectorite, the consumption of heat-resistant inorganic oxide and/or its precursor and auxiliary agent makes rectorite: heat-resistant inorganic oxide: the weight ratio in the element auxiliary agent is 45-94.9: 5-50: 0.1-20, described auxiliary agent is the compound of Mn, perhaps is one or both the mixture in the compound of the compound of the compound of Mn and P and Ce;
First slurries are mixed making beating with zeolite, make second slurries,, desciccate is mixed making beating with zeolite and water, make second slurries perhaps with first slurry dried;
With second slurry dried, make catalyst for cracking heavy oil.
Catalyst of the present invention has outstanding anti-metallicity, the ability of particularly anti-nickel, vanadium and calcium when being used for the residual oil cracking reaction; And catalyst of the present invention has also improved the weight ratio of liquefied gas, gasoline and diesel oil in the product.
The specific embodiment
The invention provides a kind of catalyst, this catalyst contains zeolite and a kind of composition, wherein, said composition contains rectorite, heat-resistant inorganic oxide and auxiliary agent, gross weight with said composition is a benchmark, the content of described rectorite is 45-94.9 weight %, the content 5-50 weight % of heat-resistant inorganic oxide, content in the element auxiliary agent is 0.1-20 weight %, described auxiliary agent is the compound of Mn, perhaps is one or both the mixture in the compound of the compound of the compound of Mn and P and Ce.
Preferably, according to catalyst provided by the invention, be benchmark with the gross weight of described composition, the content of described rectorite is 55-80 weight %, the content of heat-resistant inorganic oxide is 15-40 weight %, is 1-15 weight % in the content of element auxiliary agent.
In element, more preferably under the situation, the content of auxiliary agent is for being 2-12 weight % in the described composition.
Auxiliary agent of the present invention is the compound of Mn, perhaps is one or both the mixture in the compound of the compound of the compound of Mn and P and Ce.These compounds can be inorganic or organic compounds.For example, the compound that contains manganese can be selected from the organic compound of manganese or in the inorganic compound one or more, one or more in the oxide of manganese and the manganese salt for example, described manganese salt can be the chloride of manganese, the nitrate of manganese, the phosphate of manganese, the carboxylate of manganese, is preferably one or more of acetate of nitrate, the manganese of chloride, the manganese of manganese.The compound of phosphorus can be selected from phosphoric acid, pyrophosphoric acid, phosphorous acid, ammonium phosphate, alkali-metal phosphatic one or more.The compound of cerium can be selected from one or more of chloride, nitrate, hydroxide, oxide of cerium.
Described heat-resistant inorganic oxide can be selected from as in the heat-resistant inorganic oxide of Cracking catalyst matrix and binder component one or more, as in aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, the boron oxide one or more.In preferred aluminium oxide, silica, amorphous silicon aluminium, the zirconia one or more, more preferably aluminium oxide.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
According to catalyst of the present invention, wherein, described rectorite is one or more in natural calcium type rectorite, sodium type rectorite, lithium type rectorite or the ammonia type rectorite.Described sodium type, lithium type or ammonia type rectorite can be made by calcium type rectorite remodeling.
The basal spacing of rectorite is generally 1.9-5.0nm, the preferred basal spacing d that contains the rectorite of adjuvant component of the present invention
001Value is 2.7-5.0nm, and preferably its specific area is 100-300m
2/ g.
According to catalyst provided by the invention, wherein, described zeolite is selected from the zeolite that Cracking catalyst is used always, for example, be selected from y-type zeolite, Beta zeolite, have in the zeolite of MFI structure one or more, described y-type zeolite can be one or more in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of phosphorous and/or rare earth, phosphorous and/or rare earth; The zeolite of the described MFI of having structure can be the zeolite with MFI structure of phosphorous and/or rare earth.
Catalyst according to the invention, this catalyst can also contain clay.This clay can be 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.These clays are conventionally known to one of skill in the art.Be preferably kaolin.
Further under the preferable case, also can contain heat-resistant inorganic oxide in the catalyst of the present invention, be selected from as in the heat-resistant inorganic oxide of Cracking catalyst matrix and binder component one or more, as in aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, the boron oxide one or more.In preferred aluminium oxide, silica, amorphous silicon aluminium, zirconia, the titanium oxide one or more, more preferably aluminium oxide.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
Total amount with catalyst for cracking heavy oil is a benchmark, the content of described zeolite can be 10-95 weight %, the content of described composition can be 5-90 weight %, and the content of clay can be 0 to 85 weight %, and the content of heat-resistant inorganic oxide can be 0 to 60 weight %.Under the preferable case, total amount with catalyst for cracking heavy oil is a benchmark, and the content of described zeolite is 10-94 weight %, and the content of described composition is 5-89.9 weight %, the content of clay is greater than 0 to 85 weight %, and the content of heat-resistant inorganic oxide is greater than 0 to 60 weight %.More preferably under the situation, be benchmark with the total amount of catalyst for cracking heavy oil, the content 20-50 weight % of described zeolite, the content of described composition is 5-50 weight %, and the content of clay is greater than 0 to 70 weight %, and the content of heat-resistant inorganic oxide is 5-50 weight %.
The invention provides a kind of Preparation of catalysts method, this method comprises:
With rectorite, heat-resistant inorganic oxide and/or its precursor and water mix making beating, and under 60 ℃-80 ℃, stirred 30-120 minute, add auxiliary agent, stir more than 30 minutes, preferred 30-120 minute, make first slurries, described rectorite, heat-resistant inorganic oxide and/or its precursor, it is 10-60 weight % that the consumption of auxiliary agent and water makes the solid content of first slurries that obtain, and rectorite, the consumption of heat-resistant inorganic oxide and/or its precursor and auxiliary agent makes rectorite: heat-resistant inorganic oxide: the weight ratio in the element auxiliary agent is 45-94.9: 5-50: 0.1-20, described auxiliary agent is the compound of Mn, perhaps is one or both the mixture in the compound of the compound of the compound of Mn and P and Ce;
First slurries are mixed making beating with zeolite, make second slurries,, desciccate is mixed making beating with zeolite and water, make second slurries perhaps with first slurry dried;
With second slurry dried, make catalyst for cracking heavy oil.
Wherein, preferably, total amount with the catalyst for cracking heavy oil that makes is a benchmark, the content of the feasible catalyst mesolite that makes of the consumption of described zeolite is 10-95 weight %, and the total content of rectorite, heat-resistant inorganic oxide and auxiliary agent is 5-90 weight % in the feasible catalyst that makes of the consumption of rectorite, heat-resistant inorganic oxide and/or its precursor and auxiliary agent.
Preferably, the compound of described Mn is selected from the oxide of manganese and in the manganese salt one or more; The compound of P is selected from the phosphate of phosphoric acid, pyrophosphoric acid, phosphorous acid, ammonium, in the alkali-metal phosphate one or more; The compound of Ce is selected from one or more in the chloride, nitrate, hydroxide, oxide of cerium.
Described first slurries can be directly used in the preparation catalyst, also can be used further to prepare catalyst behind the first drying and moulding.It is 20-45 weight % that the consumption of preferred rectorite, heat-resistant inorganic oxide and/or its precursor, auxiliary agent and water makes the content of solids in the slurries.
Total amount with the catalyst for cracking heavy oil that makes is a benchmark, the content of the feasible catalyst mesolite that makes of the consumption of described zeolite is 10-95 weight %, and rectorite, heat-resistant inorganic oxide and auxiliary agent total content are 5-90 weight % in the feasible catalyst that makes of the consumption of rectorite, heat-resistant inorganic oxide and/or its precursor and auxiliary agent.
Preferably, also add clay when first slurries are mixed making beating with zeolite, the consumption of each material makes, gross weight with the catalyst that makes is a benchmark, the content of described zeolite is 10-94 weight %, and the content of described composition is 5-89.9 weight %, and the content of clay is greater than 0 to 85 weight %.
Among the preparation method of first slurries provided by the invention, the order by merging of each material does not have specific (special) requirements, for example, after rectorite and heat-resistant inorganic oxide and/or its precursor can being mixed, mixes with water again; Also can mix with heat-resistant inorganic oxide and/or its precursor again after rectorite and the water mixing.
Under the preferable case, when being mixed making beating with zeolite, first slurries also add heat-resistant inorganic oxide and/or its precursor, the consumption of each material makes, gross weight with the catalyst that makes is a benchmark, the content of described zeolite is 10-94 weight %, the content of described composition is 5-89.9 weight %, and the content of described heat-resistant inorganic oxide is greater than 0 to 60 weight %.
The precursor of described heat-resistant inorganic oxide refers in described catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminium oxide can be selected from hydrated alumina and/or aluminium colloidal sol; Described hydrated alumina is selected from one or more in boehmite (boehmite), false boehmite (boehmite), the hibbsite.The precursor of silica can be selected from Ludox, one or more in silicon gel and 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.The precursor of other heat-resistant inorganic oxide can be selected from its hydroxide, as the hydroxide of zirconium and titanium, in the boric acid one or more.Preferred hydrated alumina of the precursor of described heat-resistant inorganic oxide and/or aluminium colloidal sol.
Drying is a prior art described in the Preparation of catalysts method of the present invention, is preferably spray-drying, exhaust temperature be 160-220 ℃.Spray-drying gained catalyst also can carry out roasting, and the temperature of roasting is 350-800 ℃, is preferably 400-650 ℃, and the time of roasting is 0.5-6 hour, is preferably 1-4 hour; Described roasting can be carried out in any atmosphere, for example carries out in air.
Catalyst provided by the invention can be used as the cracking hydrocarbon oil catalyst, can also be as cocatalyst for cracking.When as co-catalyst, the content of described catalyst in the catalytic cracking catalyst mixture is 5-50 weight %.
The following examples will the invention will be further described, but not thereby limiting the invention.
Among the embodiment, rectorite derives from rectorite ore deposit, Zhongxiang City, Hubei, and its solid content is 86.7 weight %; Kaolin is produced by Suzhou kaolin company, and solid content is 82 weight %; Alumina content in the aluminium colloidal sol is 21 weight %; The acidification pseudo-boehmite solid content is 12 weight %.Used overstable gamma zeolite DASY produces for the Shandong catalyst plant, solid content 95.7%, and lattice constant is
In weight percent content, Na
2O content is 1.3%, RE
2O
3Content is 2.5%; Phosphorous Y zeolite PREHY produces for the Shandong catalyst plant, solid content 92.4%, and lattice constant is
In weight percent content, Na
2O content is 1.5%, RE
2O
3Content is 8.5%.Rare earth exchanged Y zeolite REY produces for the Shandong catalyst plant, solid content 97.5%, and lattice constant is
In weight percent content, Na
2O content is 1.6%, RE
2O
3Content is 18.2%.The concentration of hydrochloric acid is 36 weight %, and specification is a chemical pure.
Embodiment 1-4 illustrates that modification provided by the invention is tired and takes off native preparation method.
Embodiment 1
In 5.4 kilograms of decationized Y sieve water, add 16.2 kg aluminium colloidal sols and mix, under stirring condition, add 7.1 kilograms rectorite, be heated to 60 ℃ and stir after 30 minutes, add 1138 gram manganese chloride (MnCl again
24H
2O, Beijing chemical reagents corporation produces), stir after 60 minutes, obtain the slurries that solid content is 35 weight %, be T1.
Embodiment 2
In 8.6 kilograms of decationized Y sieve water, add 7.6 kg aluminium colloidal sols and mix, under stirring condition, add 8.8 kilograms rectorite, be heated to 65 ℃ and stir after 30 minutes, add 1365 gram manganese chloride (MnCl again
24H
2O, Beijing chemical reagents corporation produces) and 276 gram phosphoric acid (chemical pure, Beijing chemical reagents corporation produces), stir after 60 minutes, obtain the slurries that solid content is 40 weight %, be T2.
Embodiment 3
In 6.7 kilograms of decationized Y sieve water, add 10.5 kg aluminium colloidal sols and mix, under stirring condition, add 7.8 kilograms rectorite, be heated to 70 ℃ and stir after 30 minutes, add 1650 gram cerium chloride (CeCl again
36H
2O, Beijing chemical reagents corporation produces) and 455 gram manganese chloride (MnCl
24H
2O, Beijing chemical reagents corporation produces), stir after 60 minutes, obtain the slurries that solid content is 40 weight %, be T3.
Embodiment 4
In 8.1 kilograms of decationized Y sieve water, add 8.6 kg aluminium colloidal sols and mix, under stirring condition, add 8.3 kilograms rectorite, be heated to 75 ℃ and stir after 30 minutes, add 1031 gram cerium chloride (CeCl again
36H
2O, Beijing chemical reagents corporation produces), 414 gram phosphoric acid (chemical pure, Beijing chemical reagents corporation produces) and 455 gram manganese chloride (MnCl
24H
2O, Beijing chemical reagents corporation produces), stir after 60 minutes, obtain the slurries that solid content is 40 weight %, be T4.
Embodiment 5-10 illustrates method for preparing catalyst provided by the invention.
Embodiment 5
Get 2.29 kilograms in rectorite slurries (T1) that contain the auxiliary agent component, add 2.86 kg aluminium colloidal sols, 3.66 kilograms of kaolin, 16.67 kilograms acidification pseudo-boehmite successively, making beating, add 3.25 kilograms of PREHY molecular sieves, 0.615 kilogram of REY molecular sieve and 7.71 kilograms of decationized Y sieve water again and mix the slurries that form, stirred 30 minutes, with the slurries spray drying forming that obtains, 500 ℃ of roastings were washed after 1.5 hours, obtained catalytic cracking catalyst C1 then.
Embodiment 6
Get 3.75 kilograms in rectorite slurries (T2) that contain the auxiliary agent component, add 2.86 kg aluminium colloidal sols, 2.80 kilograms of kaolin, 16.67 kilograms acidification pseudo-boehmite successively, making beating, add 3.13 kilograms of DASY molecular sieves, 613 gram ZRP-1 molecular sieves and 7.21 kilograms of deionized waters again and mix the slurries that form, stirred 30 minutes, with the slurries spray drying forming that obtains, 500 ℃ of roastings were washed after 1.5 hours, obtained catalytic cracking catalyst C2 then.
Embodiment 7
Get 6.25 kilograms in rectorite slurries (T2) that contain the auxiliary agent component, add 2.38 kg aluminium colloidal sols, 1.83 kilograms of kaolin, 16.67 kilograms acidification pseudo-boehmite successively, making beating, add 3.25 kilograms of PREHY molecular sieves, 0.308 kilogram of REY molecular sieve, 204 gram ZRP-1 molecular sieves and 6.15 kilograms of slurries that the deionized waters mixing forms again, stirred 30 minutes, with the slurries spray drying forming that obtains, 500 ℃ of roastings were washed after 1.5 hours, obtained catalytic cracking catalyst C3 then.
Embodiment 8
Get 3.75 kilograms in rectorite slurries (T3) that contain the auxiliary agent component, add 2.86 kg aluminium colloidal sols, 3.41 kilograms of kaolin, 12.50 kilograms acidification pseudo-boehmite successively, making beating, add 3.76 kilograms of DASY molecular sieves and 10.75 kilograms of slurries that the deionized waters mixing forms again, stirred 30 minutes, with the slurries spray drying forming that obtains, 500 ℃ of roastings were washed after 1.5 hours, obtained catalytic cracking catalyst C4 then.
Embodiment 9
Get 5.00 kilograms in rectorite slurries (T3) that contain the auxiliary agent component, add 2.86 kg aluminium colloidal sols, 3.41 kilograms of kaolin, 12.50 kilograms acidification pseudo-boehmite successively, making beating, add 3.18 kilograms of REY molecular sieves and 10.0 kilograms of slurries that the deionized waters mixing forms again, stirred 30 minutes, with the slurries spray drying forming that obtains, 500 ℃ of roastings were washed after 1.5 hours, obtained catalytic cracking catalyst C5 then.
Embodiment 10
Get 3.75 kilograms in rectorite slurries (T4) that contain the auxiliary agent component, add 2.86 kg aluminium colloidal sols, 3.41 kilograms of kaolin, 12.50 kilograms acidification pseudo-boehmite successively, making beating, add 1.25 kilograms of DASY molecular sieves, 2.16 kilograms of PREHY molecular sieves, 0.410 kilogram of REY molecular sieve and 10.69 kilograms of deionized waters again and mix the slurries that form, stirred 30 minutes, with the slurries spray drying forming that obtains, 500 ℃ of roastings were washed after 1.5 hours, obtained catalytic cracking catalyst C6 then.
Comparative Examples 1
The method that provides according to embodiment among the CN1175086C 1 prepares Cracking catalyst, obtains contrast medium D1.D1 has following composition: with the total catalyst weight benchmark, and rectorite content 20.0 weight %, kaolin content 14.0 weight %, binder content 28.0 weight % (calculating) with alumina content, y-type zeolite content is 38.0 weight %.
Comparative Examples 2
The method that provides according to embodiment among the CN1211608A 1 prepares Cracking catalyst, obtains contrast medium D2.D2 has following composition: with the total catalyst weight benchmark, and rectorite content 20.0 weight %, kaolin content 14.0 weight %, binder content 28.0 weight % (calculating) with alumina content, y-type zeolite content is 38.0 weight %.
Comparative Examples 3
The method that provides according to embodiment among the 200610169674.X 3 prepares Cracking catalyst.
(1) 5.17 kilograms of decationized Y sieve water, 1035 milliliters re chloride and 1.73 kilograms of rectorites are mixed, stirs after 30 minutes, add 667 gram aluminum phosphate colloidal sols, continue stirring 90 minutes, make the slurries that solid content is 25 weight %.
(2) 2.37 kilograms of kaolin, 2.23 kilograms of aluminum phosphate colloidal sol, 10.8 kilograms acidifying aluminium stone will be added in the slurries of step (1) gained, making beating, add 5.1 kilograms of y-type zeolites and 10.8 kilograms of slurries that deionized water forms again, stirred 30 minutes, again with the slurries spray drying forming that obtains, 400 ℃ of following roastings 3 hours obtain contrast medium D3.
Embodiment 11
Present embodiment illustrates the catalytic cracking performance of catalyst for cracking heavy oil provided by the invention.
Light oil microactivity is estimated: adopt the standard method of RIPP92-90 (to see volumes such as " petrochemical industry analytical method " (RIPP test method) Yang Cuiding, Science Press, the nineteen ninety publication) light oil microactivity of assess sample, the catalyst loading amount is 5.0g, reaction temperature is 460 ℃, feedstock oil is boiling range 235-337 ℃ of huge port light diesel fuel, and product is made up of gas chromatographic analysis, forms according to product to calculate light oil microactivity.
Light oil microactivity (MA)=(being lower than gasoline output+gas yield+coke output of 216 ℃ in the product)/charging total amount * 100%
Residual oil cracking performance evaluation condition: catalyst is earlier at 800 ℃, and 100% steam aging 4 hours is estimated on ACE (fixed fluidized bed) device then, and feedstock oil is Wuhan mixed material oil (character sees Table 1), 500 ℃ of reaction temperatures, and agent weight of oil ratio is 6.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Yield of light oil=yield of gasoline+diesel yield
Estimate the catalyst C1-C6 of embodiment 5-10 preparation according to the method described above respectively, reaction result is listed in table 2.
Comparative Examples 4
The catalytic cracking performance of following Comparative Examples explanation contrast medium.
Adopt the method identical to estimate the catalytic cracking performance of comparative catalyst D1-D3 respectively, the results are shown in table 2 with embodiment 11.
Embodiment 12
Present embodiment illustrates the anti-metallicity of catalyst for cracking heavy oil provided by the invention.
With catalyst C1, C2, C5 and C6 impregnated in nickel naphthenate (1000ppm) respectively, in the kerosin of aphthenic acids vanadium (1000ppm) and calcium naphthenate (1000ppm), make catalyst C1, C2, nickel on C5 and the C6, vanadium and calcium reach 1000ppm respectively, sample number into spectrum behind the dipping is respectively C1w, C2w, C5w and C6w, with C1w, C2w, C5w and C6w are at 800 ℃, 100% steam aging 4 hours, on ACE (fixed fluidized bed) device, estimate then, feedstock oil is Wuhan mixed material oil (character sees Table 1), 500 ℃ of reaction temperatures, agent weight of oil ratio is 8.The results are shown in Table 3.
Comparative Examples 5
Handle catalyst D1, D2 and D3 according to the method identical, and use and embodiment 12 identical modes are estimated to D1w, D2w and the D3w that obtains with embodiment 12.The results are shown in Table 3.
Table 1
| ACE estimates | |
| Feedstock oil | Wuhan mixed material oil |
| Density (20 ℃), g/cm 3 | ??0.9044 |
| Refractive power (70 ℃) | ??1.5217(20℃) |
| Viscosity (100 ℃) mm 2/s | ??9.96 |
| Freezing point, ℃ | ??40 |
| Aniline point, ℃ | ??95.8 |
| ??C??m％??H??m％??S??m％??N??m％ | ??85.98??12.86??0.55??0.18 |
| Carbon residue m% | ??3.0 |
| ACE estimates | |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% | ??243??294??316??395??429??473??- |
Table 2
Table 3
| Catalyst | ??C1w | ??C2w | ??C5w | ??C6w | ??D1w | ??D2w | ??D3w |
| Product distributes, w% | |||||||
| Dry gas | ??1.73 | ??1.9 | ??1.8 | ??1.67 | ??1.89 | ??1.86 | ??1.84 |
| Liquefied gas | ??11.76 | ??17.44 | ??12.75 | ??13.02 | ??13.54 | ??12.74 | ??12.06 |
| Coke | ??7.22 | ??7.27 | ??7.21 | ??7.18 | ??7.39 | ??7.42 | ??7.40 |
| Gasoline | ??51.05 | ??45.12 | ??50.09 | ??50.45 | ??47.16 | ??48.08 | ??49.16 |
| Diesel oil | ??16.86 | ??16.59 | ??16.74 | ??16.61 | ??17.67 | ??17.21 | ??17.02 |
| Heavy oil | ??11.38 | ??11.68 | ??11.41 | ??11.07 | ??12.35 | ??12.69 | ??12.53 |
| Add up to | ??100.00 | ??100.00 | ??100.00 | ??100.00 | ??100.00 | ??100.00 | ??100.00 |
| Conversion ratio, w% | ??71.13 | ??71.73 | ??71.85 | ??72.32 | ??69.98 | ??70.98 | ??70.45 |
| Liquefied gas+gasoline+diesel oil, w% | ??79.67 | ??79.15 | ??79.58 | ??80.08 | ??78.37 | ??78.03 | ??78.13 |
From table 2 data as can be seen, compare with D3 with catalyst D1, the D2 that Comparative Examples provides, catalyst for cracking heavy oil provided by the invention has the total weight percent of higher liquefied gas, gasoline and diesel oil.
As can be seen from Table 3, compare with D3 with catalyst D1, D2 that Comparative Examples provides, catalyst for cracking heavy oil provided by the invention still shows higher conversion ratio after pollution, have the total weight percent of higher liquefied gas, gasoline and diesel oil, illustrates that its anti-metal ability is stronger.
Claims (13)
1. catalyst for cracking heavy oil, this catalyst contains zeolite and a kind of composition, wherein, said composition contains rectorite, heat-resistant inorganic oxide and auxiliary agent, gross weight with said composition is a benchmark, the content of described rectorite is 45-94.9 weight %, the content of heat-resistant inorganic oxide is 5-50 weight %, content in the element auxiliary agent is 0.1-20 weight %, described auxiliary agent is the compound of Mn, perhaps is one or more the mixture in the compound of the compound of the compound of Mn and P and Ce.
2. catalyst according to claim 1, wherein, the compound of described Mn is selected from the oxide of manganese and in the manganese salt one or more; The compound that the compound of P is selected from phosphate, one or more Ce in the alkali-metal phosphate of phosphoric acid, pyrophosphoric acid, phosphorous acid, ammonium is selected from one or more in the chloride of cerium, nitrate, hydroxide, the oxide.
3. catalyst according to claim 1, wherein, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, the boron oxide.
4. catalyst according to claim 1 wherein, is a benchmark with the total amount of catalyst for cracking heavy oil, and the content of described zeolite is 10-95 weight %, and the content of described composition is 5-90 weight %.
5. catalyst according to claim 1 wherein, also contains clay in this catalyst, total amount with catalyst for cracking heavy oil is a benchmark, the content of described zeolite is 10-94 weight %, and the content of described composition is 5-89.9 weight %, and the content of clay is greater than 0 to 85 weight %.
6. catalyst according to claim 5, wherein, described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
7. catalyst according to claim 1, wherein, this catalyst also contains heat-resistant inorganic oxide, total amount with catalyst for cracking heavy oil is a benchmark, the content of described zeolite is 10-94 weight %, the content of described composition is 5-89.9 weight %, and the content of heat-resistant inorganic oxide is greater than 0 to 60 weight %.
8. catalyst according to claim 7, wherein, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica, amorphous silicon aluminium, zirconia, titanium oxide, the boron oxide.
9. the preparation method of the described catalyst for cracking heavy oil of claim 1, this method comprises:
With rectorite, heat-resistant inorganic oxide and/or its precursor and water mix making beating, and under 60 ℃-80 ℃, stirred 30-120 minute, add auxiliary agent, stir more than 30 minutes, make first slurries, described rectorite, heat-resistant inorganic oxide and/or its precursor, it is 10-60 weight % that the consumption of auxiliary agent and water makes the solid content of first slurries that obtain, and rectorite, the consumption of heat-resistant inorganic oxide and/or its precursor and auxiliary agent makes rectorite: heat-resistant inorganic oxide: the weight ratio in the element auxiliary agent is 45-94.9: 5-50: 0.1-20, described auxiliary agent is the compound of Mn, perhaps is one or more the mixture in the compound of the compound of the compound of Mn and P and Ce;
First slurries are mixed making beating with zeolite, make second slurries,, desciccate is mixed making beating with zeolite and water, make second slurries perhaps with first slurry dried;
With second slurry dried, make catalyst for cracking heavy oil.
10. method according to claim 9, wherein, the consumption of each material makes, is benchmark with the total amount of the catalyst for cracking heavy oil that makes, and the content of zeolite is 10-95 weight %, and the total content of rectorite, heat-resistant inorganic oxide and auxiliary agent is 5-90 weight %.
11. method according to claim 9, wherein, the compound of described Mn is selected from the oxide of manganese and in the manganese salt one or more; The compound of P is selected from the phosphate of phosphoric acid, pyrophosphoric acid, phosphorous acid, ammonium, in the alkali-metal phosphate one or more; The compound of Ce is selected from one or more in the chloride, nitrate, hydroxide, oxide of cerium.
12. method according to claim 9, wherein, when being mixed making beating with zeolite, first slurries also add heat-resistant inorganic oxide and/or its precursor, the consumption of each material makes, gross weight with the catalyst that makes is a benchmark, the content of described zeolite is 10-94 weight %, and the content of described composition is 5-89.9 weight %, and the content of described heat-resistant inorganic oxide is greater than 0 to 60 weight %.
13. method according to claim 9, wherein, when being mixed making beating with zeolite, first slurries also add clay, the consumption of each material makes, gross weight with the catalyst that makes is a benchmark, the content of described zeolite is 10-94 weight %, and the content of described composition is 5-89.9 weight %, and the content of clay is greater than 0 to 85 weight %.
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