CN102974383B - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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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 phosphorus-containing and rare-earth-containing Y-type 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, assists in achieving relatively high conversion rate, and assists in producing gasoline with relatively low olefin content.
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 as vacuum distillate or more heavy constituent residual oil catalyst exist under react, be converted into the high value added products such as liquefied gas, gasoline, diesel oil, in this process, conventionally need to use the catalysis material with high cracking activity.Micro-pore zeolite catalysis material, owing to having good shape selective catalysis performance and very high cracking reaction activity, is widely used in petroleum refining and processing industry.Along with the requirement, particularly crude oil of the aspect of exhaustion and environmental protection etc. day by day of petroleum resources become heavy growth trend and the market wilderness demand to light-end products increasingly, in PETROLEUM PROCESSING industry, more and more pay attention to the deep processing to heavy oil and residual oil.
In recent years, along with continuing to increase of environmental protection dynamics, in the state III of up-to-date promulgation in 2011 gasoline standard, require gasoline olefin volume fraction to be not more than 30%, the state IV standards of carrying out in some big cities requires gasoline olefin volume fraction to be not more than 28% especially, and in China's gasoline blending component approximately 80% from catalytically cracked gasoline, be a quick feasible approach so alkene agent falls in exploitation gasoline fraction.
For improving conversion ratio, strengthen heavy oil conversion performance, reduce the further conversion of intermediate oil and naphtha simultaneously, traditional micro porous molecular sieve catalysis material is because its duct is less, larger raw molecule is demonstrated to obvious restriction diffusion, make the not too suitable catalytic cracking that is applied to the heavy distillate such as heavy oil and residual oil of simple micro porous molecular sieve catalysis material, thereby need to use aperture larger, reactant molecule is not had to diffusion-restricted, and there is the material of higher cracking activity.Therefore, mesoporous and research and development macropore catalysis material are more and more subject to people's attention.
Aspect mesoporous catalyst exploitation, US5492874A discloses a kind of Cracking catalyst taking 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.
In addition, CN1854258A discloses a kind of fluid cracking catalyst, this fluid cracking catalyst contain 3-20 % by weight through acid-treated mesoporous silica-alumina materials, wherein, this preparation method through acid-treated mesoporous silica-alumina materials comprises: according to the method preparation process ammonium exchange of CN1565733A but without acid-treated mesoporous silica-alumina materials, then, this mesoporous silica-alumina materials is made to slurries, and add wherein hydrochloric acid solution to carry out acidification at approximately 60 DEG C, thereby make through acid-treated mesoporous silica-alumina materials.But this fluid cracking catalyst is needing further raising to the conversion ratio in the process of RFCC processing; And, in the preparation process of mesoporous silica-alumina materials wherein, adopt traditional ammonium exchange process, wherein ammonium salt mostly is ammonium sulfate, ammonium chloride, ammonium nitrate etc., and ammonium salt ratio used 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 object of this invention is to provide a kind of catalytic cracking catalyst, this catalytic cracking catalyst has higher conversion ratio in heavy oil catalytic cracking process, and can obtain the gasoline fraction that olefin(e) centent is lower, in addition in the preparation process of the mesoporous silica-alumina materials in this catalytic cracking catalyst without carrying out ammonium exchange, can not produce ammonia nitrogen waste water, the preparation process that makes this catalytic cracking catalyst relatively environmental protection and cost lower.
The invention provides a kind of catalytic cracking catalyst, this catalytic cracking catalyst contains cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, described mesoporous silica-alumina materials is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange is mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3,
Described cracking activity constituent element contains phosphorous and Y zeolite rare earth, and described phosphorous and Y zeolite rare earth is made by the method comprising the following steps:
(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve
2o content is 1-5 % by weight, RE
2o
3content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;
(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P
2o
5: water=1: (0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;
(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, and the method comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, obtain sodium oxide content not higher than the mesoporous silica-alumina materials of 0.2 % by weight, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) the described mesoporous silica-alumina materials obtaining in cracking activity constituent element, step (1), clay and binding agent are mixed to making beating, then spray successively and be dried, wash, filter and be dried, wherein, described cracking activity constituent element contains phosphorous and Y zeolite rare earth, and described phosphorous and Y zeolite rare earth is made by the method comprising the following steps:
(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve
2o content is 1-5 % by weight, RE
2o
3content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;
(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P
2o
5: water=1: (0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;
(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere.
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 can obtain the gasoline fraction that olefin(e) centent is lower.
And, in the preparation method of described catalytic cracking catalyst of the present invention, in the preparation process of described mesoporous silica-alumina materials, without carrying out ammonium exchange, can not produce ammonia nitrogen waste water, the preparation process that makes this catalytic cracking catalyst relatively environmental protection and cost lower.
In addition, in the preparation process of described mesoporous silica-alumina materials, only need to use an inorganic acid to carry out ion-exchange and can obtain the mesoporous silica-alumina materials of sodium oxide content lower than 0.2 % by weight, thereby reduced production cost and improved production efficiency.
Brief description of the drawings
Fig. 1 is the X-ray diffracting spectrum of the mesoporous silica-alumina materials in described catalytic cracking catalyst of the present invention.
Detailed description of the invention
The invention provides a kind of catalytic cracking catalyst, this catalytic cracking catalyst contains cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, described mesoporous silica-alumina materials is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange is mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3,
Described cracking activity constituent element contains phosphorous and Y zeolite rare earth, and described phosphorous and Y zeolite rare earth is made by the method comprising the following steps:
(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve
2o content is 1-5 % by weight, RE
2o
3content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;
(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P
2o
5: water=1: (0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;
(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere.
In the present invention, in the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.In the present invention, refer to the weight of roasting after 1 hour under the condition of approximately 800 DEG C in the weight of butt.
In the preferred case, the weight ratio of the 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 of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the weight of the 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 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 one or more in sulfuric acid, hydrochloric acid and nitric acid.
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 described slurries and mix contact, described slurries can be added yet and in inorganic acid, mix contact.Under preferable case, inorganic acid is joined and in described slurries, mixes 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 conventional ion-exchange condition.Under preferable case, the temperature of described contact is 30-80 DEG C, more preferably 40-70 DEG C; 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 boehmite crystal phase structure, and its X-ray diffracting spectrum as shown in Figure 1.And, in described mesoporous silica-alumina materials, taking 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, the described mesoporous silica-alumina materials without ion-exchange can be the conventional various mesoporous silica-alumina materials without any ion-exchange in this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to conventional method, and its preparation method for example can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic terminal pH is 7-11; Then according to SiO
2: Al
2o
3=1: weight ratio (0.6-9) adds silicon source, aging 1-10 hour at room temperature to 90 DEG C, then filters.In the present invention, the sial sediment obtaining after described filtration can directly be used as the described mesoporous silica-alumina materials without ion-exchange, also can be dried and/or roasting after as the described mesoporous silica-alumina materials without ion-exchange.
In the present invention, described aluminium source can be the conventional various aluminium source using, this area, and described aluminium source for example can be for being selected from one or more in aluminum nitrate, aluminum sulfate or aluminium chloride.
In the present invention, described silicon source can be the conventional various silicon source using, this area, and described silicon source can be for example at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and silicon gel.
In the present invention, described aqueous slkali can be the conventional various aqueous slkalis that use in this area, for example, can be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.
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 separately from the above-mentioned material of enumerating, but, having at least in common described aluminium source, aqueous slkali and silicon source is a kind of for containing the raw material of sodium, thereby ensures 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 taking the sodium content of sodium oxide molybdena as 0.5-15 % by weight.And in described catalytic cracking catalyst of the present invention, in the described mesoporous silica-alumina materials of preparing without the mesoporous silica-alumina materials of ion-exchange described in adopting, be generally below 0.2 % by weight in the sodium content of sodium oxide molybdena.
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 conventional catalytic cracking catalyst.Under preferable case, taking the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is taking the content of butt as 10-70 % by weight, described mesoporous silica-alumina materials is taking the content of butt as 1-20 % by weight, described clay is taking the content of butt as 10-70 % by weight, and described binding agent is taking the content of butt as 10-60 % by weight.
In further preferred situation, taking the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is taking the content of butt as 10-45 % by weight, described mesoporous silica-alumina materials is taking the content of butt as 2-15 % by weight, described clay is taking the content of butt as 20-40 % by weight, and described binding agent is taking the content of butt as 20-50 % by weight.
In the present invention, in order further to improve described catalytic cracking catalyst of the present invention at the catalytic cracking activity in the process of RFCC, to obtain the conversion ratio of further raising, and further reduce the olefin(e) centent in the gasoline obtaining, under preferable case, in described cracking activity constituent element, in the gross weight of described cracking activity constituent element, the content of the Y zeolite of described phosphorous and rare earth is 60-100 % by weight, more preferably 78-100 % by weight.In the present invention, the content of the Y zeolite of the described phosphorous and rare earth in described cracking activity constituent element is in butt.
In the present invention, the concrete preparation process of the Y zeolite of described phosphorous and rare earth can be with reference to CN1353086A, particularly embodiment 1-8 wherein.
According to described catalytic cracking catalyst provided by the invention, described cracking activity constituent element can also contain containing at least one in the DASY molecular sieve of rare earth, REY molecular sieve and MFI structure molecular screen.Under preferable case, in described cracking activity constituent element, in the gross weight of described cracking activity constituent element, the content of the Y zeolite of described phosphorous and rare earth is 60-99.9 % by weight, more preferably 78-99 % by weight; The total content of described DASY molecular sieve, REY molecular sieve and MFI structure molecular screen containing rare earth is 0.1-40 % by weight, more preferably 1-22 % by weight.
In the present invention, the described DASY molecular sieve containing rare earth is the hydro-thermal super stable molecular sieve containing rare earth, wherein with RE
2o
3the content of rare earth of (rare earth oxide) meter can be 1.5-3.0 % by weight.The described DASY molecular sieve containing rare earth can be various commercially available prod, for example, can be the DASY2.0 molecular sieve purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry.
In the present invention, 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 purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry.
In the present invention, in described MFI structure molecular screen taking the molar ratio computing of oxide without 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 in table, the represented relative intensity value of each symbol is as follows
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 molecular sieve intracrystalline.The faujasite seeds containing rare earth that rare earth uses 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
27in Al NMR spectrum, have corresponding to Al (4Si) coordination spectrum peak (being that Al is derived from by oxygen and four Si atoms formation tetrahedral structures), that chemical shift is 55ppm, and have corresponding to Al (4P) coordination spectrum peak (being that Al atom forms tetrahedral structures by oxygen and four P atoms), that chemical shift is 39ppm; This molecular sieve exists
31in P NMR spectrum, have corresponding to P (4Al) coordination and (exist PO
4tetrahedron and adjacent AlO
4tetrahedral interaction), chemical shift is-the spectrum peak of 29ppm.
In the preferred case, the phosphorus in described MFI structure molecular screen is uniformly distributed in molecular sieve crystalline phase.The analysis result of transmission electron microscope-energy dispersion spectrum (TEM-EDS) shows that the phosphorus content during phosphorus content in any single crystal grain and molecule sieve nest are is mutually close.
Described MFI structure molecular screen is 4-5 to the absorption weight ratio of n-hexane and cyclohexane, is that 40 DEG C, adsorption time are 3 hours, Adsorption Phase pressure P/P at adsorption temp
0under the condition of=0.20-0.25, this molecular sieve to the adsorbance of n-hexane be 98-105 milligram/gram, to the adsorbance of cyclohexane be 20-25 milligram/gram.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, what described MFI structure molecular screen can be prepared according to conventional method obtains, and concrete preparation method also can be with reference to patent application CN1147420A, particularly embodiment 1-6 wherein.
In the present invention, described clay can be the conventional various clays that use in catalytic cracking catalyst, for example can be for being selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
In the present invention, described binding agent can be the conventional various binding agents that use in catalytic cracking catalyst, for example, can, for being selected from one or more in Ludox, aluminium colloidal sol and boehmite, be preferably the double aluminium binder of aluminium colloidal sol and boehmite.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, and the method comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, obtain sodium oxide content not higher than the mesoporous silica-alumina materials of 0.2 % by weight, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) the described mesoporous silica-alumina materials obtaining in cracking activity constituent element, step (1), clay and binding agent are mixed to making beating, then spray successively and be dried, wash, filter and be dried, wherein, described cracking activity constituent element contains phosphorous and Y zeolite rare earth, and described phosphorous and Y zeolite rare earth is made by the method comprising the following steps:
(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve
2o content is 1-5 % by weight, RE
2o
3content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;
(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P
2o
5: water=1: (0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;
(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere.
According to the preparation method of described catalytic cracking catalyst provided by the invention, in step (1), in the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.
In the preferred case, the weight ratio of the 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 the preparation method of described catalytic cracking catalyst provided by the invention, described inorganic acid can be the inorganic acid of various routines, for example can be for being selected from one or more in sulfuric acid, hydrochloric acid and nitric acid.
According to the preparation method of described catalytic cracking catalyst 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 described slurries and mix contact, also described slurries can be added and in inorganic acid, mix contact.Under preferable case, inorganic acid is joined and in described slurries, mixes contact.
According to the preparation method of described catalytic cracking catalyst provided by the invention, in step (1), the condition that described slurries are contacted with inorganic acid preferably includes: Contact Temperature is 30-80 DEG C, more preferably 40-70 DEG C; Be 0.2-2 hour, more preferably 0.3-1.5 hour time of contact.
According to the preparation method of described catalytic cracking catalyst provided by the invention, in step (1), the described mesoporous silica-alumina materials without ion-exchange can be the conventional various mesoporous silica-alumina materials without any ion-exchange in this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to conventional method, and its preparation method for example can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic terminal pH is 7-11; Then according to SiO
2: Al
2o
3=1: weight ratio (0.6-9) adds silicon source, aging 1-10 hour at room temperature to 90 DEG C, then filters.In the present invention, the sial sediment obtaining after described filtration can directly be used as the described mesoporous silica-alumina materials without ion-exchange, also can be dried and/or roasting after as the described mesoporous silica-alumina materials without ion-exchange.Described aluminium source, silicon source and aqueous slkali all with above describe identical.
According to the preparation method of described catalytic cracking catalyst provided by the invention, in step (2), by described cracking activity constituent element, the described mesoporous silica-alumina materials obtaining in step (1), clay and binding agent mix making beating, and follow-up spraying is dry, washing, filter and be dried, 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, in CN1727445A and CN1098130A, there is detailed description, here introduce in the lump in the present invention with for referencial use.
According to the preparation method of described catalytic cracking catalyst 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 obtaining in described cracking activity constituent element, 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 above describe identical.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, phosphorous and Y zeolite rare earth makes according to the method for embodiment in CN1353086A 1;
DASY2.0 molecular sieve is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry;
REY molecular sieve is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry;
MFI structure molecular screen makes according to the method for embodiment 1 in patent application CN1147420A;
Aluminium colloidal sol is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry;
Kaolin is purchased from Suzhou China Kaolin Co., Ltd;
Boehmite is purchased from Shandong Aluminum Plant;
Na in mesoporous silica-alumina materials
2o, Al
2o
3, SiO
2content for x-ray fluorescence method measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).
Embodiment 1
The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
(1) preparation of mesoporous silica-alumina materials
Be 90g Al by 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 stream add in continuous gel formation still, and 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 keeps plastic pH value, and plastic temperature is 55 DEG C; Collect the slurries 300ml after plastic, under stirring condition, adding 127ml content is 60g SiO
2the sodium silicate solution of/L, be warming up to 80 DEG C aging 4 hours, then filter.
The sial sediment obtaining after filtering is mixed to making beating taking weight ratio as 1: 12 with water, again by hydrochloric acid solution by described sial sediment (butt): HCl=1: 0.14 weight ratio adds in the slurries that obtain after making beating, at 60 DEG C, sial sediment is carried out to acid exchange to remove sodium ion wherein, be 30 minutes swap time, then filter, and the sediment obtaining after filtering is dried and roasting successively, thereby obtain mesoporous silica-alumina materials SSA-1.This mesoporous silica-alumina materials sample has 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
The boehmite of 20 weight portions in butt is mixed to making beating with deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, acid aluminum ratio (weight) is 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively in the kaolinic slurries of 29 weight portion of butt, in the aluminium colloidal sol (Al of 8 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, stir 20 minutes, add wherein more afterwards the slurries in the Y zeolite of the described phosphorous and rare earth of 38 weight portions of butt, the dry microspherical catalyst of making of spraying after continuing to stir.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then at 60 DEG C with (NH
4)
2sO
4washing ((NH
4)
2sO
4: microspherical catalyst: H
2o=0.05: 1: 10) to Na
2o content is less than 0.25 % by weight, finally uses deionized water drip washing, after filtration, at 110 DEG C, dries, and obtains catalytic cracking catalyst C1.
Embodiment 2-7
The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
Prepare catalytic cracking catalyst according to the method for embodiment 1 respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, the Y zeolite of described phosphorous and rare earth, described DASY2.0 molecular sieve, described REY molecular sieve, described MFI structure molecular screen, the inventory in butt of boehmite and aluminium colloidal sol is as shown in table 2 below respectively, wherein, for the situation of the embodiment that has used different kinds of molecules to sieve, this different kinds of molecules sieve mixes with other component with the form of mixed molecular sieve slurries, the inventory of each component is all in weight portion, thereby make respectively catalytic cracking catalyst C2-C7.
Table 2
Comparative example 1
(1) preparation of mesoporous silica-alumina materials
Make mesoporous silica-alumina materials SH-SA-1 according to the method for implementing 1 in CN 1854258A.
(2) preparation of catalytic cracking catalyst
Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 2, difference is, replaces described mesoporous silica-alumina materials SSA-1 with described mesoporous silica-alumina materials SH-SA-1, thereby makes catalytic cracking catalyst DC1.
Comparative example 2-3
Prepare catalytic cracking catalyst according to the method for comparative example 1 respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, the described inventory in the butt phosphorous and Y zeolite of rare earth, described DASY2.0 molecular sieve, described REY molecular sieve, described MFI structure molecular screen, boehmite and aluminium colloidal sol are distinguished as shown in table 3 below, wherein the inventory of each component is all in weight portion, thereby makes respectively catalytic cracking catalyst DC2-DC3.
Table 3
Embodiment 8
The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
Prepare catalytic cracking catalyst according to the method for embodiment 2, difference is, in step (1), the sial sediment obtaining after filtering is mixed to making beating taking weight ratio as 1: 12 with water, again by hydrochloric acid solution by described sial sediment (butt): HCl=1: 0.07 weight ratio adds in the slurries that obtain after making beating, at 100 DEG C, sial sediment is carried out to acid exchange to remove sodium ion wherein, be 18 minutes swap time, then filter, and the sediment obtaining after filtering is dried and roasting successively, thereby obtain mesoporous silica-alumina materials, this mesoporous silica-alumina materials sample has boehmite crystal phase structure, 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
2, then make catalytic cracking catalyst C8 with the mesoporous silica-alumina materials of so preparation.
Embodiment 9
The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.
Prepare catalytic cracking catalyst according to the method for embodiment 2, difference is, in step (1), the sial sediment obtaining after filtering is mixed to making beating taking weight ratio as 1: 12 with water, again by hydrochloric acid solution by described sial sediment (butt): HCl=1: 0.16 weight ratio adds in the slurries that obtain after making beating, at 25 DEG C, sial sediment is carried out to acid exchange to remove sodium ion wherein, be 90 minutes swap time, then filter, and the sediment obtaining after filtering is dried and roasting successively, thereby obtain mesoporous silica-alumina materials, this mesoporous silica-alumina materials sample has boehmite crystal phase structure, 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
2, then make catalytic cracking catalyst C9 with the mesoporous silica-alumina materials of so preparation.
Test case
Respectively by above-mentioned catalytic cracking catalyst C1-C9 and DC1-DC3, under 800 DEG C, the condition of 100% water vapour aging 17 hours, be filled in afterwards the reactivity worth of evaluating catalytic cracking catalyst in small fixed flowing bed ACE device (purchased from KTI company of the U.S.), amount of fill is 9g.Then, be that 500 DEG C, air speed are under 16h-1, oil ratio (weight) condition that is 6 in reaction temperature, using mixed the force shown in table 4 three feedstock oils as feedstock oil, inject described small fixed flowing bed ACE device and carry out catalytic cracking reaction.The composition of analytical reactions product, and calculate conversion ratio according to following formula, result is as shown in table 5 below.
According to the olefin(e) centent in the methods analyst gasoline of ASTM D6293-98, result is as shown in table 5 below.
Table 4
| Feedstock oil | Military mixed three feedstock oils |
| Density (20 DEG C), g/cm 3 | 0.9044 |
| Viscosity (100 DEG C), mm 2/s | 9.96 |
| Four components, % by weight | |
| Saturated hydrocarbons | 60.7 |
| Aromatic hydrocarbons | 20.6 |
| Colloid | 16.3 |
| Asphalitine | 2.4 |
| C % by weight | 85.98 |
| H % by weight | 12.86 |
| S % by weight | 0.55 |
| N % by weight | 0.18 |
| Carbon residue, % by weight | 3 |
| Boiling range, DEG C | |
| Initial boiling point | 243 |
| 5％ | 294 |
| 10％ | 316 |
| 30％ | 395 |
| 50％ | 429 |
| 70％ | 473 |
Table 5
In above-mentioned table 5, by by embodiment 2 and comparative example 1, embodiment 4 and comparative example 2, and embodiment 5 compares respectively and can find out with comparative example 3, described catalytic cracking catalyst of the present invention shows relatively high catalytic cracking activity in to the process of RFCC processing, higher conversion ratio can be obtained, and the gasoline that olefin(e) centent is lower can be obtained.
Claims (17)
1. a catalytic cracking catalyst, this catalytic cracking catalyst contains 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 comprising the following steps: the mesoporous silica-alumina materials without ion-exchange is mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1:5-30:0.03-0.3, described without in the mesoporous silica-alumina materials of ion-exchange taking the sodium content of sodium oxide molybdena as 0.5-15 % by weight, the preparation method of the described mesoporous silica-alumina materials without ion-exchange comprises: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH of plastic terminal is 7-11, then according to SiO
2: Al
2o
3=1:(0.6-9) weight ratio add silicon source, aging 1-10 hour at room temperature to 90 DEG C, then filters,
Described cracking activity constituent element contains phosphorous and Y zeolite rare earth, and described phosphorous and Y zeolite rare earth is made by the method comprising the following steps:
(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve
2o content is 1-5 % by weight, RE
2o
3content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;
(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P
2o
5: water=1:(0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;
(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere.
2. catalytic cracking catalyst according to claim 1, wherein, described inorganic acid is selected from one or more in sulfuric acid, hydrochloric acid and nitric acid.
3. catalytic cracking catalyst according to claim 1, wherein, the weight ratio of the 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 the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:8-15:0.07-0.16.
5. according to the catalytic cracking catalyst described in any one in claim 1-4, wherein, the Contact Temperature of described slurries and inorganic acid is 30-80 DEG C, and be 0.2-2 hour time of contact.
6. catalytic cracking catalyst according to claim 1, wherein, described mesoporous silica-alumina materials has boehmite crystal phase structure, taking the anhydrous chemical expression of oxide weight as (0-0.2) Na
2o (40-90) Al
2o
3(10-60) SiO
2.
7. catalytic cracking catalyst according to claim 1, wherein, described cracking activity constituent element also contains containing at least one in the DASY molecular sieve of rare earth, REY molecular sieve and MFI structure molecular screen.
8. catalytic cracking catalyst according to claim 7, wherein, in described MFI structure molecular screen taking the molar ratio computing of oxide without 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.
9. according to the catalytic cracking catalyst described in claim 7 or 8, wherein, in described cracking activity constituent element, in the gross weight of described cracking activity constituent element, the content of the Y zeolite of described phosphorous and rare earth is 60-99.9 % by weight, and the total content of described DASY molecular sieve, REY molecular sieve and MFI structure molecular screen containing rare earth is 0.1-40 % by weight.
10. according to the catalytic cracking catalyst described in claim 1 or 7, wherein, taking the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is taking the content of butt as 10-70 % by weight, described mesoporous silica-alumina materials is taking the content of butt as 1-20 % by weight, described clay is taking the content of butt as 10-70 % by weight, and described binding agent is taking the content of butt as 10-60 % by weight.
11. catalytic cracking catalysts according to claim 10, wherein, taking the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is taking the content of butt as 10-45 % by weight, described mesoporous silica-alumina materials is taking the content of butt as 2-15 % by weight, described clay is taking the content of butt as 20-40 % by weight, and described binding agent is taking the content of butt as 20-50 % by weight.
The preparation method of 12. 1 kinds of catalytic cracking catalysts, the method comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, obtain sodium oxide content not higher than the mesoporous silica-alumina materials of 0.2 % by weight, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3;
(2) the described mesoporous silica-alumina materials obtaining in cracking activity constituent element, step (1), clay and binding agent are mixed to making beating, then spray successively and be dried, wash, filter and be dried, wherein, described cracking activity constituent element contains phosphorous and Y zeolite rare earth, and described phosphorous and Y zeolite rare earth is made by the method comprising the following steps:
(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve
2o content is 1-5 % by weight, RE
2o
3content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;
(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P
2o
5: water=1:(0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;
(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere;
Wherein, the preparation method of the described mesoporous silica-alumina materials without ion-exchange comprises: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH of plastic terminal is 7-11; Then according to SiO
2: Al
2o
3=1:(0.6-9) weight ratio add silicon source, aging 1-10 hour at room temperature to 90 DEG C, then filters.
13. methods according to claim 12, wherein, in step (1), the Contact Temperature of described slurries and inorganic acid is 30-80 DEG C, be 0.2-2 hour time of contact.
14. methods according to claim 12, wherein, described cracking activity constituent element also contains containing at least one in the DASY molecular sieve of rare earth, REY molecular sieve and MFI structure molecular screen.
15. methods according to claim 14, wherein, in described MFI structure molecular screen taking the molar ratio computing of oxide without 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.
16. according to the method described in claims 14 or 15, wherein, in described cracking activity constituent element, in the gross weight of described cracking activity constituent element, the content of the Y zeolite of described phosphorous and rare earth is 60-99.9 % by weight, and the total content of described DASY molecular sieve, REY molecular sieve and MFI structure molecular screen containing rare earth is 0.1-40 % by weight.
17. according to the method described in claim 12 or 15, 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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| CN105312076B (en) * | 2014-05-29 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN106179458B (en) * | 2015-04-29 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN106179454B (en) * | 2015-04-29 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN106179476B (en) * | 2015-04-29 | 2018-08-28 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN106179475B (en) * | 2015-04-29 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN106179457B (en) * | 2015-04-29 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| 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 |
| CN108355705A (en) * | 2018-03-19 | 2018-08-03 | 湖北赛因化工有限公司 | A kind of catalyst for heavy oil catalytic cracking and preparation method thereof |
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| 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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