CN102974388A - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN102974388A CN102974388A CN2011102612704A CN201110261270A CN102974388A CN 102974388 A CN102974388 A CN 102974388A CN 2011102612704 A CN2011102612704 A CN 2011102612704A CN 201110261270 A CN201110261270 A CN 201110261270A CN 102974388 A CN102974388 A CN 102974388A
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Abstract
The invention relates to a catalytic cracking catalyst and a preparation method thereof. The catalytic cracking catalyst comprises a cracking-active component, a mesoporous silica-alumina material, clay, and a binder. The preparation method of the mesoporous silica-alumina material comprises the steps that: a mesoporous silica-alumina material without ion exchange is mixed with water, and the mixture is beaten into slurry; and the obtained slurry contacts an inorganic acid under room temperature to 100 DEG C for at least 0.2h, such that the sodium oxide content in the mesoporous silica-alumina material is no higher than 0.2wt%, wherein a weight ratio of the mesoporous silica-alumina material without ion exchange to water to inorganic acid is 1:5-30:0.03-0.3. The cracking-active component comprises 30-99wt% of magnesium-containing ultra-stable Y-type molecular sieve and 1-70wt% of at least one type of molecular sieve selected from rare-earth-containing DASY molecular sieve, REY molecular sieve, and MFI-structured molecular sieve. During a catalytic cracking treatment process upon raw oil with relatively high basic nitrogen content, the catalytic cracking catalyst shows relatively high catalytic cracking activity, and assists in achieving relatively high conversion rate and especially relatively high diesel oil yield.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, and the preparation method of this catalytic cracking catalyst.
Background technology
Catalytic cracking (FCC) is important crude oil secondary processing process, occupies very important status in petroleum refining industry.In catalytic cracking process, heavy end such as vacuum distillate or the residual oil that divides of more recombinating react in the presence of catalyst, be converted into the high value added products such as liquefied gas, gasoline, diesel oil, in this process, usually need to use the catalysis material with high cracking activity.The micro-pore zeolite catalysis material is widely used in petroleum refining and the processing industry owing to have good shape selective catalysis performance and very high cracking reaction activity.Along with the requirement, particularly crude oil of the aspect such as day by day exhaustion and environmental protection etc. of petroleum resources becomes heavy growth trend and market increasingly to the wilderness demand of light-end products, in PETROLEUM PROCESSING industry, more and more pay attention to the deep processing to heavy oil and residual oil.
For improving conversion ratio, strengthen heavy oil conversion performance, reduce simultaneously the further conversion of intermediate oil and naphtha, traditional micro porous molecular sieve catalysis material is because its duct is less, larger raw molecule is demonstrated obvious restriction diffusion, so that the not too suitable catalytic cracking that is applied to the heavy distillates such as heavy oil and residual oil of simple micro porous molecular sieve catalysis material, thereby need to use the aperture larger, reactant molecule is not had diffusion-restricted, and have the material of higher cracking activity.Therefore, the mesoporous and research and development macropore catalysis material more and more are subject to people's attention.
Recently, along with day by day heaviness, the in poor quality of catalytically cracked stock, mixing the inferior raw material such as coking wax oil (CGO) has become the important channel that the refinery enlarges catalytically cracked material source and enhancing efficiency by relying on tapping internal latent power.Compare with the direct current wax oil, wax tailings is the fcc raw material inferior that a kind of nitrogen content, arene content and gum level are higher, saturated hydrocarbon content is lower, increase mixing of wax tailings and refine the normal operating that has a strong impact on catalytic cracking unit than regular meeting, cause conversion ratio to reduce, product distributes and obviously worsens.
Studies show that, nitride in the wax tailings especially basic nitrogen compound is the immediate cause that causes this consequence, basic nitrogen compound is owing to contain lone pair electrons, have very strong absorption and complex performance, therefore be easy to catalyst on acid centre interact, cause the activity decline of catalyst.And nitrogen-containing compound is easier to be adsorbed on the acid centre of catalyst than polycyclic aromatic hydrocarbon, easily forms the coking point, promotes green coke, and namely nitrogen-containing compound can be regarded as the coke precursor that is easier to adsorb.
Cause on the problem of catalyst activity reduction overcoming basic nitrogen compound, the method for taking just like the process means of mentioning among CN1088246A, US7744745 and the US5660716, use the method for the catalyst of alkali resistance nitrogen compound, remove the method for basic nitrogen compound etc. such as the complexing of mentioning among the US4846962.
Aspect the catalyst of alkali resistance nitrogen compound, more research is, catalyst modification comprises that element modified regulating catalyst is acid, the phosphorus modification is arranged, transition metal modification, alkali-earth metal modified etc., element modified modulation product distributes, acid treatment regulating catalyst performance, the anti-nitrogen auxiliary agent (comprising liquid adjuvants) that exploitation adds etc.US4747935A discloses a kind of aluminium oxide and a kind of acid clay additive of phosphoric acid load, and it is mixed use with the regenerative agent of catalytic cracking, can process the higher feedstock oil of basic nitrogen.US5492874A discloses a kind of Cracking catalyst take modified meerschaum as active component, and the specific area of this active component is at 50～600m
2/ g, average pore size is between 20～110 dusts.The function of this component is to catch basic nitrogen compound in catalytic cracking process.
In addition, CN1854258A discloses a kind of fluid cracking catalyst, this fluid cracking catalyst contain the 3-20 % by weight through acid-treated mesoporous silica-alumina materials, wherein, this preparation method through acid-treated mesoporous silica-alumina materials comprises: the method according to CN1565733A prepares through the ammonium exchange but without acid-treated mesoporous silica-alumina materials, then, this mesoporous silica-alumina materials is made slurries, and under about 60 ℃, carry out acidification to wherein adding hydrochloric acid solution, thereby make through acid-treated mesoporous silica-alumina materials.Yet this fluid cracking catalyst is still waiting further raising at the conversion ratio that the feedstock oil higher to basic nitrogen compound content carries out in the process that catalytic cracking processes; And, in the preparation process of mesoporous silica-alumina materials wherein, adopted traditional ammonium exchange process, wherein ammonium salt mostly is ammonium sulfate, ammonium chloride, ammonium nitrate etc., and the used ratio of ammonium salt is relatively high in ammonium friendship process, increased to a certain extent the production cost of mesoporous silica-alumina materials, the discharge capacity of ammonia nitrogen waste water also obviously improves simultaneously, therefore causes the raising of environmental protection of enterprise pressure and the increase of post processing cost.
Summary of the invention
The purpose of this invention is to provide a kind of catalytic cracking catalyst, this catalytic cracking catalyst has higher conversion ratio in the feedstock oil higher to basic nitrogen compound content (being the feedstock oil of about 900-1500 μ g/g such as basic n content) carries out the process of catalytic cracking processing, and can obtain higher diesel yield, need not to carry out in addition the ammonium exchange in the preparation process of the mesoporous silica-alumina materials in this catalytic cracking catalyst, can not produce ammonia nitrogen waste water so that the preparation process of this catalytic cracking catalyst relatively environmental protection and cost are lower.
The invention provides a kind of catalytic cracking catalyst, this catalytic cracking catalyst contains the cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, described mesoporous silica-alumina materials is made by the method that may further comprise the steps: will mix making beating with water without the mesoporous silica-alumina materials of ion-exchange, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour under room temperature to 100 ℃, so that the sodium oxide content in the described mesoporous silica-alumina materials is not higher than 0.2 % by weight, wherein, described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3;
Gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 30-99 % by weight and the second molecular sieve component of 1-70 % by weight, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium, described the second molecular sieve component is at least a in DASY molecular sieve, REY molecular sieve and the MFI structure molecular screen that contains rare earth, wherein
In the described super-stable Y molecular sieves that contains magnesium take the content of magnesium of magnesia as the 0.1-25 % by weight;
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, and the method may further comprise the steps:
(1) will mix making beating with water, obtain slurries without the mesoporous silica-alumina materials of ion-exchange, again gained slurries and inorganic acid are contacted at least 0.2 hour under room temperature to 100 ℃, obtain the mesoporous silica-alumina materials that sodium oxide content is not higher than 0.2 % by weight, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) with the cracking activity constituent element, the described mesoporous silica-alumina materials that obtains in the step (1), clay and binding agent mix making beating, then carry out successively spray-drying, washing, filter and drying, wherein, gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 30-99 % by weight and the second molecular sieve component of 1-70 % by weight, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium, described the second molecular sieve component is the DASY molecular sieve that contains rare earth, at least a in REY molecular sieve and the MFI structure molecular screen, wherein
In the described super-stable Y molecular sieves that contains magnesium take the content of magnesium of magnesia as the 0.1-25 % by weight;
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
Described catalytic cracking catalyst of the present invention is specially adapted to RFCC, particularly, when the basic nitrogen compound content in the feedstock oil is higher, described catalytic cracking catalyst of the present invention can show higher catalytic cracking activity in the process of RFCC, can obtain higher conversion ratio and diesel yield.
And, in the preparation method of described catalytic cracking catalyst of the present invention, need not to carry out ammonium exchange in the preparation process of described mesoporous silica-alumina materials, can not produce ammonia nitrogen waste water so that the preparation process of this catalytic cracking catalyst relatively environmental protection and cost are lower.
In addition, only need to use an inorganic acid to carry out ion-exchange in the preparation process of described mesoporous silica-alumina materials and can obtain the mesoporous silica-alumina materials that sodium oxide content is lower than 0.2 % by weight, thereby reduced production cost and improved production efficiency.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the mesoporous silica-alumina materials in the described catalytic cracking catalyst of the present invention.
The specific embodiment
The invention provides a kind of catalytic cracking catalyst, this catalytic cracking catalyst contains the cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, described mesoporous silica-alumina materials is made by the method that may further comprise the steps: will mix making beating with water without the mesoporous silica-alumina materials of ion-exchange, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour under room temperature to 100 ℃, so that the sodium oxide content in the described mesoporous silica-alumina materials is not higher than 0.2 % by weight, wherein, described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3;
Gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 30-99 % by weight and the second molecular sieve component of 1-70 % by weight, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium, described the second molecular sieve component is at least a in DASY molecular sieve, REY molecular sieve and the MFI structure molecular screen that contains rare earth, wherein
In the described super-stable Y molecular sieves that contains magnesium take the content of magnesium of magnesia as the 0.1-25 % by weight;
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
In the present invention, in the weight ratio without mesoporous silica-alumina materials, water and the inorganic acid of ion-exchange, described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.In the present invention, the weight in butt refers in the weight of roasting after 1 hour under about 800 ℃ condition.
In the preferred case, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is preferably 1: (6-20): (0.05-0.2), and more preferably 1: (8-15): (0.07-0.16).In the present invention, in the weight ratio without mesoporous silica-alumina materials, water and the inorganic acid of ion-exchange, the weight of described mesoporous silica-alumina materials without ion-exchange is in its butt; The weight of described inorganic acid refers to the weight of inorganic acid composition, and for example, when described inorganic acid adds fashionablely with the form of aqueous hydrochloric acid solution, the weight of described inorganic acid refers to the weight of HCl in the aqueous hydrochloric acid solution.
In the present invention, described inorganic acid can be the inorganic acid of various routines, for example can be for being selected from sulfuric acid, hydrochloric acid and the nitric acid one or more.
In the process of the described mesoporous silica-alumina materials of preparation, the mode that described slurries are contacted with inorganic acid does not have special requirement, inorganic acid can be joined in the described slurries to mix contact, described slurries can be added in the inorganic acid yet and mix contact.Under the preferable case, inorganic acid joined in the described slurries mix contact.
In the process of the described mesoporous silica-alumina materials of preparation, the condition that described slurries are contacted with inorganic acid can be the ion-exchange condition of routine.Under the preferable case, the temperature of described contact is 30-80 ℃, more preferably 40-70 ℃; The time of described contact is 0.2-2 hour, more preferably 0.3-1.5 hour.
In the present invention, described mesoporous silica-alumina materials preferably has the boehmite crystal phase structure, and its X-ray diffracting spectrum as shown in Figure 1.And, in described mesoporous silica-alumina materials, take the anhydrous chemical expression of oxide weight as (0-0.2) Na
2O (40-90) Al
2O
3(10-60) SiO
2
In the process of the described mesoporous silica-alumina materials of preparation, described mesoporous silica-alumina materials without ion-exchange can be this area various mesoporous silica-alumina materials without any ion-exchange commonly used.Described mesoporous silica-alumina materials without ion-exchange can prepare according to the method for routine, and its preparation method for example can comprise: aluminium source and aqueous slkali are neutralized into glue under room temperature to 85 ℃, becoming glue terminal point pH is 7-11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ lower wearing out 1-10 hour, then filters.In the present invention, the sial sediment that obtains after the described filtration can directly be used as described mesoporous silica-alumina materials without ion-exchange, also it can be carried out being used as described mesoporous silica-alumina materials without ion-exchange after drying and/or the roasting.
In the present invention, described aluminium source can be conventional various aluminium source of using, this area, and described aluminium source for example can be for being selected from aluminum nitrate, aluminum sulfate or the aluminium chloride one or more.
In the present invention, described silicon source can be conventional various silicon source of using, this area, and what described silicon source for example can be in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and the silicon gel is at least a.
In the present invention, described aqueous slkali can be the conventional various aqueous slkalis that use in this area, for example can be in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and the sodium hydroxide solution one or more.
In the process of the described mesoporous silica-alumina materials without ion-exchange of preparation, although described aluminium source, silicon source and aqueous slkali can suitably be selected from the above-mentioned material of enumerating separately, yet, having at least in common described aluminium source, aqueous slkali and the silicon source is a kind of for containing the raw material of sodium, thereby guarantees that the described mesoporous silica-alumina materials without ion-exchange of so preparation has the meso-hole structure of appropriate size.
In the present invention, described without in the mesoporous silica-alumina materials of ion-exchange take the sodium content of sodium oxide molybdena as the 0.5-15 % by weight.And in described catalytic cracking catalyst of the present invention, adopt that the sodium content in sodium oxide molybdena is generally below 0.2 % by weight in the described mesoporous silica-alumina materials of described mesoporous silica-alumina materials preparation without ion-exchange.
According to described catalytic cracking catalyst provided by the invention, there is no particular limitation for the content of described cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, and their content range all can be determined according to the composition of the catalytic cracking catalyst of routine.Under the preferable case, take the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is take the content of butt as the 10-70 % by weight, described mesoporous silica-alumina materials is take the content of butt as the 1-20 % by weight, described clay is take the content of butt as the 10-70 % by weight, and described binding agent is take the content of butt as the 10-60 % by weight.
In the further preferred situation, take the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is take the content of butt as the 10-45 % by weight, described mesoporous silica-alumina materials is take the content of butt as the 2-15 % by weight, described clay is take the content of butt as the 20-40 % by weight, and described binding agent is take the content of butt as the 20-50 % by weight.
In the present invention, carry out catalytic cracking activity in the process of catalytic cracking in order further to improve described catalytic cracking catalyst of the present invention at the heavy oil higher to basic nitrogen compound content, with the conversion ratio that obtains further to improve, and further improve the activity that mink cell focus is converted into diesel oil, with the diesel yield that obtains further to improve, under the preferable case, in the gross weight of described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 45-95 % by weight and the second molecular sieve component of 5-55 % by weight.In the present invention, the content of the component in the described cracking activity constituent element is in its butt.
In the present invention, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium.Take the content of magnesium of magnesia as the 0.1-25 % by weight, be preferably the 0.5-25 % by weight in the described super-stable Y molecular sieves that contains magnesium.
The described super-stable Y molecular sieves that contains magnesium can prepare according to the method for routine, a kind of preparation method wherein for example can comprise: will dissolve or the magnesium compound after abundant wet-milling (for example be selected from magnesia, magnesium chloride, magnesium sulfate and the magnesium nitrate at least a) is dispersed in super-stable Y molecular sieves (USY molecular sieve) slurries, add or do not add ammoniacal liquor, mix rear drying and roasting; Another kind of preparation method for example can comprise: the super-stable Y molecular sieves after abundant wet-milling (USY molecular sieve) is dispersed in the solution of magnesium compound (for example be selected from magnesium chloride, magnesium sulfate and the magnesium nitrate at least a), add filter successively after ammoniacal liquor mixes, wash, drying and roasting.
The above-mentioned preparation method's of the described super-stable Y molecular sieves that contains magnesium specific implementation process for example can be with reference to CN1297018A, particularly wherein embodiment 1-5.
In the present invention, described the first molecular sieve component is at least a in DASY molecular sieve, REY molecular sieve and the MFI structure molecular screen that contains rare earth.
The described DASY molecular sieve that contains rare earth is the hydro-thermal super stable molecular sieve that contains rare earth, wherein with RE
2O
3The content of rare earth of (rare earth oxide) meter can be the 1.5-3.0 % by weight.The described DASY molecular sieve that contains rare earth can be various commercially available prod, for example can be the DASY2.0 molecular sieve available from China Petrochemical Industry's catalyst asphalt in Shenli Refinery.
Described REY molecular sieve is rare earth Y type molecular sieve, and it can be various commercially available REY zeolite products, for example can be available from China Petrochemical Industry's catalyst asphalt in Shenli Refinery.
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
The x-ray diffraction spectra data of described MFI structure molecular screen are as shown in table 1 below, and the represented relative intensity of each symbol value is as shown in table 1 below in the table, in following table 1, and VS:80-100%; S:60-80%; M:40-60%; W:20-40%; VW:＜20%.
Table 1
| D value (* 10 -1Nanometer) | I/I 0 |
| 11.2±0.2 | VS |
| 10.1±0.2 | M |
| 9.8±0.2 | VW |
| 3.85±0.04 | VS |
| 3.81±0.04 | S |
| 3.75±0.04 | W |
| 3.72±0.04 | M |
| 3.65±0.04 | M |
| 3.60±0.04 | W |
In described MFI structure molecular screen, rare earth is included in the molecular sieve intracrystalline.Rare earth employed faujasite seeds that contains rare earth during from Zeolite synthesis.
In described MFI structure molecular screen, the aluminum chemistry of phosphorus in framework of molecular sieve is combined, and this molecular sieve exists
27Have in the Al NMR spectrum corresponding to Al (4Si) coordination (be Al be derived from by oxygen and four Si atoms form tetrahedral structures), chemical shift is the spectrum peak of 55ppm, and have corresponding to Al (4P) coordination (being that the Al atom is by oxygen and four P atoms formation tetrahedral structures), chemical shift is the spectrum peak of 39ppm; This molecular sieve exists
31Then have corresponding to P (4Al) coordination in the P NMR spectrum and (namely exist PO
4Tetrahedron and adjacent AlO
4Tetrahedral interaction), chemical shift is-the spectrum peak of 29ppm.
In the preferred case, the phosphorus in the described MFI structure molecular screen is uniformly distributed in the molecular sieve crystalline phase.The analysis result of transmission electron microscope-energy dispersion spectrum (TEM-EDS) shows that phosphorus content and the molecule sieve nest phosphorus content in mutually in any single crystal grain is close.
Described MFI structure molecular screen is 4-5 to the absorption weight ratio of n-hexane and cyclohexane, is that 40 ℃, adsorption time are 3 hours, Adsorption Phase pressure P/P at adsorption temp
0Under the condition of=0.20-0.25, this molecular sieve is 98-105 milligram/gram to the adsorbance of n-hexane, is 20-25 milligram/gram to the adsorbance of cyclohexane.This absorption weight ratio (4-5) is apparently higher than this ratio (2-25) of ZSM-5 zeolite.
In the present invention, the specific descriptions of described MFI structure molecular screen can be with reference to patent application CN1147420A.
In the present invention, described MFI structure molecular screen can be according to the obtaining of the method for routine preparation, and concrete preparation method also can be with reference to patent application CN1147420A, particularly wherein embodiment 1-6.
In the present invention, described clay can be the conventional various clays that use in the catalytic cracking catalyst, for example can be for being selected from kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and the bentonite one or more.
In the present invention, described binding agent can be the conventional various binding agents that use in the catalytic cracking catalyst, for example can for being selected from Ludox, aluminium colloidal sol and the boehmite one or more, be preferably the double aluminium binder of aluminium colloidal sol and boehmite.
In the present invention, described catalytic cracking catalyst can also contain and adds rare earth.The described rare earth that adds is to form by extra adding rare earth chloride in the process of the described catalytic cracking catalyst of preparation.In described catalytic cracking catalyst, the described rare earth that adds is usually with rare earth oxide (RE
2O
3) form exist.Take the butt weight of described catalytic cracking catalyst as benchmark, the described content that adds rare earth can be the 0-3 % by weight, is preferably the 0.5-2 % by weight.
In the present invention, rare earth element refers to the rare earth element of the various routines that relate in the catalytic cracking catalyst field, such as thinking lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium etc.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, and the method may further comprise the steps:
(1) will mix making beating with water, obtain slurries without the mesoporous silica-alumina materials of ion-exchange, again gained slurries and inorganic acid are contacted at least 0.2 hour under room temperature to 100 ℃, obtain the mesoporous silica-alumina materials that sodium oxide content is not higher than 0.2 % by weight, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) with the cracking activity constituent element, the described mesoporous silica-alumina materials that obtains in the step (1), clay and binding agent mix making beating, then carry out successively spray-drying, washing, filter and drying, wherein, gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 30-99 % by weight and the second molecular sieve component of 1-70 % by weight, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium, described the second molecular sieve component is the DASY molecular sieve that contains rare earth, at least a in REY molecular sieve and the MFI structure molecular screen, wherein
In the described super-stable Y molecular sieves that contains magnesium take the content of magnesium of magnesia as the 0.1-25 % by weight;
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
According to described method provided by the invention, in step (1), in the weight ratio without mesoporous silica-alumina materials, water and the inorganic acid of ion-exchange, described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.
In the preferred case, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is preferably 1: (6-20): (0.05-0.2), and more preferably 1: (8-15): (0.07-0.16).
According to described method provided by the invention, described inorganic acid can be the inorganic acid of various routines, for example can be for being selected from sulfuric acid, hydrochloric acid and the nitric acid one or more.
According to described method provided by the invention, in step (1), the mode that described slurries are contacted with inorganic acid does not have special requirement, inorganic acid can be joined in the described slurries to mix contact, described slurries can be added in the inorganic acid yet and mix contact.Under the preferable case, inorganic acid joined in the described slurries mix contact.
According to described method provided by the invention, in step (1), the condition that described slurries are contacted with inorganic acid preferably includes: Contact Temperature is 30-80 ℃, more preferably 40-70 ℃; Be 0.2-2 hour time of contact, more preferably 0.3-1.5 hour.
According to described method provided by the invention, in step (1), described mesoporous silica-alumina materials without ion-exchange can be this area various mesoporous silica-alumina materials without any ion-exchange commonly used.Described mesoporous silica-alumina materials without ion-exchange can prepare according to the method for routine, and its preparation method for example can comprise: aluminium source and aqueous slkali are neutralized into glue under room temperature to 85 ℃, becoming glue terminal point pH is 7-11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ lower wearing out 1-10 hour, then filters.In the present invention, the sial sediment that obtains after the described filtration can directly be used as described mesoporous silica-alumina materials without ion-exchange, also it can be carried out being used as described mesoporous silica-alumina materials without ion-exchange after drying and/or the roasting.Described aluminium source, silicon source and aqueous slkali all with preamble describe identical.
According to described method provided by the invention, in step (2), with described cracking activity constituent element, the described mesoporous silica-alumina materials that obtains in the step (1), clay and binding agent mix making beating, and follow-up spray-drying, washing, filter and drying, the implementation method of these operations all can adopt conventional method to implement, their specific implementation method is for example at patent application CN1916166A, CN1362472A, CN1727442A, CN1132898C, detailed description is arranged among CN1727445A and the CN1098130A, introduce in the lump here among the present invention with for referencial use.
According to described method provided by the invention, in step (2), in butt, the weight ratio of the addition of described mesoporous silica-alumina materials, described clay and the described binding agent that obtains in described cracking activity constituent element, the step (1) can be (10-70): (1-20): (10-70): (10-60), be preferably (10-45): (2-15): (20-40): (20-50).Described cracking activity constituent element, clay and binding agent all with preamble describe identical.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the super-stable Y molecular sieves that contains magnesium makes according to the method for embodiment among the CN1297018A 1;
The DASY2.0 molecular sieve is produced by China Petrochemical Industry's catalyst asphalt in Shenli Refinery;
The REY molecular sieve is produced by China Petrochemical Industry's catalyst asphalt in Shenli Refinery;
The MFI structure molecular screen makes according to the method for embodiment 1 among the patent application CN1147420A;
Aluminium colloidal sol is produced by China Petrochemical Industry's catalyst asphalt in Shenli Refinery;
Kaolin is available from Suzhou China Kaolin Co., Ltd;
Boehmite is available from Shandong Aluminum Plant;
Rare earth chloride is available from Xitu Hi-Tech skill limited company of Baogang;
Na in the mesoporous silica-alumina materials
2O, Al
2O
3, SiO
2Content measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with x-ray fluorescence method.
Embodiment 1
Present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
(1) preparation of mesoporous silica-alumina materials
Be 90g Al with concentration
2O
3The Al of/L
2(SO
4)
3Solution and concentration are 102g Al
2O
3/ L, causticity are than the NaAlO that is 1.7
2Solution and stream add in the continuous gel formation still, and the colloid generating kettle effective volume is 200ml, Al
2(SO
4)
3The flow of solution is 20ml/min, regulates NaAlO
2It is 9 that flow is held in glue pH value, and becoming the glue temperature is 55 ℃; Be gathered into the slurries 300ml behind the glue, adding 127ml content under stirring condition is 60g SiO
2The sodium silicate solution of/L is warming up to 80 ℃ and wore out 4 hours, then filters.
The sial sediment that obtains after filtering was mixed making beating with water take weight ratio as 1: 12, again with hydrochloric acid solution by described sial sediment (butt): HCl=1: 0.14 weight ratio adds in the slurries that obtain after the making beating, under 60 ℃, the sial sediment is carried out the acid exchange to remove sodium ion wherein, be 30 minutes swap time, then filter, and the sediment that will obtain after will filtering carries out drying and roasting successively, thereby obtains mesoporous silica-alumina materials SSA-1.This mesoporous silica-alumina materials sample has the boehmite crystal phase structure, and its X-ray diffraction spectral line as shown in Figure 1; Its elementary analysis weight chemical composition is 0.06Na
2O73.8Al
2O
326.0SiO
2
(2) preparation of catalytic cracking catalyst
To mix making beating with deionized water in the boehmite of 18 weight portions of butt, and to add concentration in the slurries that obtain be the hydrochloric acid peptization of 36 % by weight, acid aluminum ratio (weight) is 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively the kaolinic slurries of 32 weight portions contain in butt, in the aluminium colloidal sol (Al of 9 weight portions of butt
2O
3Content is 21.5 % by weight) and in the slurries of the mesoporous silica-alumina materials SSA-1 of 5 weight portions of butt, stirred 20 minutes, contain the super-stable Y molecular sieves of magnesium and in the mixed serum of the described REY molecular sieve of 10 weight portions of butt, spray-drying is made microspherical catalyst after continuing to stir to wherein adding in 26 weight portions of butt described more afterwards.This microspherical catalyst is 500 ℃ of lower roastings 1 hour, lower to (NH at 60 ℃ again
4)
2SO
4Washing ((NH
4)
2SO
4: microspherical catalyst: H
2O=0.05: 1: 10) to Na
2O content is used deionized water drip washing at last less than 0.25 % by weight, in 110 ℃ of lower oven dry, obtains catalytic cracking catalyst C1 after filtering.
Embodiment 2-7
Present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
Method according to embodiment 1 prepares catalytic cracking catalyst respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, the described super-stable Y molecular sieves that contains magnesium, described DASY2.0 molecular sieve, described REY molecular sieve, described MFI structure molecular screen, boehmite, aluminium colloidal sol is as shown in table 2 below respectively in the inventory of rare earth oxide in inventory and the rare earth chloride of butt, wherein, described rare earth chloride carries out spray-drying after mixing making beating evenly with the slurries of other component with the form of re chloride again, the inventory of each component is all in weight portion, thereby makes respectively catalytic cracking catalyst C2-C7.
Table 2
Comparative Examples 1
(1) preparation of mesoporous silica-alumina materials
Make mesoporous silica-alumina materials SH-SA-1 according to the method for implementing 1 among the CN 1854258A.
(2) preparation of catalytic cracking catalyst
Method according to step (2) among the embodiment 1 prepares catalytic cracking catalyst, and difference is to replace described mesoporous silica-alumina materials SSA-1 with described mesoporous silica-alumina materials SH-SA-1, thereby make catalytic cracking catalyst DC1.
Comparative Examples 2-3
Method according to Comparative Examples 1 prepares catalytic cracking catalyst respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, the described super-stable Y molecular sieves that contains magnesium, described DASY2.0 molecular sieve, described REY molecular sieve, described MFI structure molecular screen, boehmite, aluminium colloidal sol is as shown in table 3 below respectively in the inventory of rare earth oxide in inventory and the rare earth chloride of butt, wherein, described rare earth chloride carries out spray-drying after mixing making beating evenly with the slurries of other component with the form of re chloride again, the inventory of each component is all in weight portion, thereby makes respectively catalytic cracking catalyst DC2-DC3.
Table 3
Embodiment 8
Present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
Method according to embodiment 1 prepares catalytic cracking catalyst, difference is, in step (1), the sial sediment that obtains after filtering was mixed making beating with water take weight ratio as 1: 5, again with hydrochloric acid solution by described sial sediment (butt): HCl=1: 0.07 weight ratio adds in the slurries that obtain after the making beating, under 70 ℃, the sial sediment is carried out the acid exchange to remove sodium ion wherein, be 18 minutes swap time, then filter, and the sediment that will obtain after will filtering carries out drying and roasting successively, thereby obtain mesoporous silica-alumina materials, this mesoporous silica-alumina materials sample has the boehmite crystal phase structure, and its X-ray diffraction spectral line as shown in Figure 1; Its elementary analysis weight chemical composition is 0.17Na
2O74.0Al
2O
325.6SiO
2Then make catalytic cracking catalyst C8 with the mesoporous silica-alumina materials of so preparation.
Embodiment 9
Present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
Method according to embodiment 1 prepares catalytic cracking catalyst, difference is, in step (1), the sial sediment that obtains after filtering was mixed making beating with water take weight ratio as 1: 12, again with hydrochloric acid solution by described sial sediment (butt): HCl=1: 0.16 weight ratio adds in the slurries that obtain after the making beating, under 40 ℃, the sial sediment is carried out the acid exchange to remove sodium ion wherein, be 90 minutes swap time, then filter, and the sediment that will obtain after will filtering carries out drying and roasting successively, thereby obtain mesoporous silica-alumina materials, this mesoporous silica-alumina materials sample has the boehmite crystal phase structure, and its X-ray diffraction spectral line as shown in Figure 1; Its elementary analysis weight chemical composition is 0.11Na
2O74.2Al
2O
325.6SiO
2Then make catalytic cracking catalyst C9 with the mesoporous silica-alumina materials of so preparation.
Test case
With above-mentioned catalytic cracking catalyst C1-C9 and DC1-DC3 process metallic pollution, so that they contain the Ni of 1000ppm and the V of 500ppm separately, then under 800 ℃, the condition of 100% water vapour aging 8 hours, be seated in afterwards the reactivity worth that catalytic cracking catalyst is provided in the fixed fluidized bed FFB device (being provided by The Earth S. A. of Sinopec Research Institute of Petro-Chemical Engineering), the amount of fill of catalyst is 150g.Then, be that 510 ℃, air speed are 16h in reaction temperature
-1, oil ratio (weight) is under 4 the condition, the catalytic mixing oil shown in the table 4 as feedstock oil, to be injected described fixed fluidized bed FFB device and carries out catalytic cracking reaction.The composition of analytical reactions product, and calculate conversion ratio according to following formula, the result is as shown in table 5 below:
Table 4
| Feedstock oil | Catalytic mixing oil |
| Density (20 ℃), g/cm 3 | 0.9334 |
| Refractive power (70 ℃) | 1.5061 |
| Four components, % by weight | |
| Saturated hydrocarbons | 55.6 |
| |
30 |
| Colloid | 14.4 |
| Asphalitine | ＜0.1 |
| Freezing point, ℃ | 34 |
| Tenor, μ g/g | |
| Ca | 3.9 |
| Fe | 1.1 |
| Na | 0.8 |
| Ni | 3.1 |
| V | 0.5 |
| Element forms, % by weight | |
| C | 86.88 |
| H | 11.94 |
| S | 0.7 |
| N | 0.27 |
| Carbon residue, % by weight | 1.77 |
| Basic nitrogen, μ g/g | 912 |
Table 5
In above-mentioned table 5, by with embodiment 1 and Comparative Examples 1, embodiment 3 and Comparative Examples 2, and embodiment 6 compares respectively and can find out with Comparative Examples 3, described catalytic cracking catalyst of the present invention shows relatively high catalytic cracking activity in the feedstock oil higher to basic n content carries out process that catalytic cracking processes, higher conversion ratio can be obtained, particularly higher diesel yield can be obtained.
Claims (15)
1. catalytic cracking catalyst, this catalytic cracking catalyst contains the cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, it is characterized in that, described mesoporous silica-alumina materials is made by the method that may further comprise the steps: will mix making beating with water without the mesoporous silica-alumina materials of ion-exchange, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour under room temperature to 100 ℃, so that the sodium oxide content in the described mesoporous silica-alumina materials is not higher than 0.2 % by weight, wherein, described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3;
Gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 30-99 % by weight and the second molecular sieve component of 1-70 % by weight, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium, described the second molecular sieve component is at least a in DASY molecular sieve, REY molecular sieve and the MFI structure molecular screen that contains rare earth, wherein
In the described super-stable Y molecular sieves that contains magnesium take the content of magnesium of magnesia as the 0.1-25 % by weight;
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
2. catalytic cracking catalyst according to claim 1, wherein, described inorganic acid is selected from one or more in sulfuric acid, hydrochloric acid and the nitric acid.
3. catalytic cracking catalyst according to claim 1, wherein, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 6-20: 0.05-0.2.
4. catalytic cracking catalyst according to claim 3, wherein, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 8-15: 0.07-0.16.
5. the described catalytic cracking catalyst of any one according to claim 1-4, wherein, the Contact Temperature of described slurries and inorganic acid is 30-80 ℃, be 0.2-2 hour time of contact.
6. catalytic cracking catalyst according to claim 1, wherein, described mesoporous silica-alumina materials has the boehmite crystal phase structure, take the anhydrous chemical expression of oxide weight as (0-0.2) Na
2O (40-90) Al
2O
3(10-60) SiO
2
7. according to claim 1 or 6 described catalytic cracking catalysts, wherein, the preparation method of described mesoporous silica-alumina materials without ion-exchange comprises: aluminium source and aqueous slkali are neutralized into glue under room temperature to 85 ℃, becoming the pH of glue terminal point is 7-11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ lower wearing out 1-10 hour, then filters.
8. the described catalytic cracking catalyst of any one according to claim 1-4, wherein, described without in the mesoporous silica-alumina materials of ion-exchange take the sodium content of sodium oxide molybdena as the 0.5-15 % by weight.
9. catalytic cracking catalyst according to claim 1, wherein, in the gross weight of described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 45-95 % by weight and the second molecular sieve component of 5-55 % by weight.
10. according to claim 1 or 9 described catalytic cracking catalysts, wherein, take the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is take the content of butt as the 10-70 % by weight, described mesoporous silica-alumina materials is take the content of butt as the 1-20 % by weight, described clay is take the content of butt as the 10-70 % by weight, and described binding agent is take the content of butt as the 10-60 % by weight.
11. catalytic cracking catalyst according to claim 10, wherein, take the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is take the content of butt as the 10-45 % by weight, described mesoporous silica-alumina materials is take the content of butt as the 2-15 % by weight, described clay is take the content of butt as the 20-40 % by weight, and described binding agent is take the content of butt as the 20-50 % by weight.
12. the preparation method of a catalytic cracking catalyst, the method may further comprise the steps:
(1) will mix making beating with water, obtain slurries without the mesoporous silica-alumina materials of ion-exchange, again gained slurries and inorganic acid are contacted at least 0.2 hour under room temperature to 100 ℃, obtain the mesoporous silica-alumina materials that sodium oxide content is not higher than 0.2 % by weight, the weight ratio of described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) with the cracking activity constituent element, the described mesoporous silica-alumina materials that obtains in the step (1), clay and binding agent mix making beating, then carry out successively spray-drying, washing, filter and drying, wherein, gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 30-99 % by weight and the second molecular sieve component of 1-70 % by weight, described the first molecular sieve component is the super-stable Y molecular sieves that contains magnesium, described the second molecular sieve component is the DASY molecular sieve that contains rare earth, at least a in REY molecular sieve and the MFI structure molecular screen, wherein
In the described super-stable Y molecular sieves that contains magnesium take the content of magnesium of magnesia as the 0.1-25 % by weight;
In the described MFI structure molecular screen take the molar ratio computing of oxide without the hydrochemical compositions expression formula as (0.01-0.25) RE
2O
3(0.005-0.02) Na
2OAl
2O
3(0.2-1.0) P
2O
5(35-120) SiO
2, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane.
13. method according to claim 12, wherein, in step (1), the Contact Temperature of described slurries and inorganic acid is 30-80 ℃, and be 0.2-2 hour time of contact.
14. method according to claim 12, wherein, in step (1), the preparation method of described mesoporous silica-alumina materials without ion-exchange comprises: aluminium source and aqueous slkali are neutralized into glue under room temperature to 85 ℃, becoming the pH of glue terminal point is 7-11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ lower wearing out 1-10 hour, then filters.
15. method according to claim 12, wherein, in butt, the weight ratio of the addition of described cracking activity constituent element, described mesoporous silica-alumina materials, described clay and described binding agent is (10-70): (1-20): (10-70): (10-60).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148984A (en) * | 2014-05-29 | 2015-12-16 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, and preparation method and application thereof |
| CN108160099A (en) * | 2016-12-07 | 2018-06-15 | 中国石油天然气股份有限公司 | A kind of catalyst for heavy oil catalytic cracking |
| CN112717961A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, and catalytic cracking catalyst and preparation method thereof |
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| CN1296860A (en) * | 1999-11-17 | 2001-05-30 | 中国石化集团齐鲁石油化工公司 | Process for preparing catalyst containing small-grain Y-molecular sieve |
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN1854258A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Cracking catalyst |
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| CN1296860A (en) * | 1999-11-17 | 2001-05-30 | 中国石化集团齐鲁石油化工公司 | Process for preparing catalyst containing small-grain Y-molecular sieve |
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN1854258A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Cracking catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148984A (en) * | 2014-05-29 | 2015-12-16 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, and preparation method and application thereof |
| CN105148984B (en) * | 2014-05-29 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN108160099A (en) * | 2016-12-07 | 2018-06-15 | 中国石油天然气股份有限公司 | A kind of catalyst for heavy oil catalytic cracking |
| CN108160099B (en) * | 2016-12-07 | 2020-09-04 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst |
| CN112717961A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, and catalytic cracking catalyst and preparation method thereof |
| CN112717961B (en) * | 2019-10-28 | 2023-04-11 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, and catalytic cracking catalyst and preparation method thereof |
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