CN102974385A - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN102974385A CN102974385A CN2011102612780A CN201110261278A CN102974385A CN 102974385 A CN102974385 A CN 102974385A CN 2011102612780 A CN2011102612780 A CN 2011102612780A CN 201110261278 A CN201110261278 A CN 201110261278A CN 102974385 A CN102974385 A CN 102974385A
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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. 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.
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 need not to carry out 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, described cracking activity constituent element contains Y zeolite, 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.
The present invention also provides a kind of preparation method of catalytic cracking catalyst, the method comprises: (1) will mix making beating, obtain slurries without the mesoporous silica-alumina materials of ion-exchange with water, 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, wherein, 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) described mesoporous silica-alumina materials, clay and the binding agent that obtains in cracking activity constituent element, the step (1) mixed making beating, then carry out successively spray-drying, washing, filtration and drying, wherein, described cracking activity constituent element contains Y zeolite.
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, 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, described catalytic cracking catalyst contains the cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, described cracking activity constituent element contains Y zeolite, 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.
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 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.
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.
According to described catalytic cracking catalyst provided by the invention, there is no particular limitation for the Y zeolite in the described cracking activity constituent element, can be the Y zeolite of various routines.Yet, 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, thereby obtain the further conversion ratio of raising, described cracking activity constituent element preferably contains the first Y zeolite of 5-70 % by weight, the second Y zeolite of 0-55 % by weight and the 3rd Y zeolite of 0-95 % by weight, and the total content of described the second Y zeolite and described the 3rd Y zeolite is the 30-95 % by weight; The first Y zeolite that more preferably contains the 10-30 % by weight, the second Y zeolite of 25-55 % by weight and the 3rd Y zeolite of 20-60 % by weight; The first Y zeolite that further preferably contains the 14-26 % by weight, the second Y zeolite of 28.5-52 % by weight and the 3rd Y zeolite of 22-57.5 % by weight.In the present invention, the part by weight of each component in the described cracking activity constituent element is all in butt.
In the present invention, described the first Y zeolite is the DASY molecular sieve 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.
In the present invention, described the second Y zeolite is the REY molecular sieve.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 present invention, in described the 3rd Y zeolite take the content of rare earth of rare earth oxide as the 12-16 % by weight, with P
2O
5The phosphorus content of meter is the 0.5-7 % by weight, this molecular sieve
31In the P MAS NMR spectrum, the percentage that chemical shift accounts for total peak area for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal is greater than 85%, this molecular sieve
27In the Al MAS NMR spectrum, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the percentage of total peak area greater than 20%.
In the preferred case, in described the 3rd Y zeolite with P
2O
5The phosphorus content of meter is the 1-3 % by weight.
In the preferred case, described the 3rd Y zeolite
31In the P MAS NMR spectrum, chemical shift accounts for the percentage of total peak area greater than 90% for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal.
In the preferred case, the lattice constant of described the 3rd Y zeolite is
In the present invention, the specific descriptions of described the 3rd Y zeolite can be with reference to patent application CN101088917A.
In the present invention, described the 3rd Y zeolite can prepare according to the method for routine, and concrete preparation method also can be with reference to patent application CN101088917A, particularly wherein embodiment 1-4.
According to described catalytic cracking catalyst provided by the invention, described cracking activity constituent element can also contain other molecular sieve except Y zeolite, such as MFI structure molecular screen, Beta molecular sieve etc.In described cracking activity constituent element, the content of described other molecular sieve can be preferably below 10 % by weight for below 20 % by weight, even is below 5 % by weight.
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, wherein, 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) described mesoporous silica-alumina materials, clay and the binding agent that obtains in cracking activity constituent element, the step (1) mixed making beating, then carry out successively spray-drying, washing, filtration and drying, wherein, described cracking activity constituent element contains Y zeolite.
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 first Y zeolite is the DASY2.0 molecular sieve, is produced by China Petrochemical Industry's catalyst asphalt in Shenli Refinery;
The second Y zeolite is the REY molecular sieve, is produced by China Petrochemical Industry's catalyst asphalt in Shenli Refinery;
The 3rd Y zeolite makes according to the method for embodiment 1 among the patent application CN101088917A;
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 20 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 kaolinic slurries of 28 weight portions in butt, in the aluminium colloidal sol (Al of 13 weight portions of butt
2O
3Content is 21.5 % by weight) and in the slurries of the mesoporous silica-alumina materials SSA-1 of 4 weight portions of butt, stirred 20 minutes, afterwards again to wherein add described the first Y zeolite in 5 weight portions of butt, in described second Y zeolite of 10 weight portions of butt with in the mixed serum of described the 3rd Y zeolite of 20 weight portions of butt, spray-drying is made microspherical catalyst after continuing to stir.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, described the first Y zeolite, described the second Y zeolite, described the 3rd Y zeolite, boehmite, aluminium colloidal sol is as shown in table 1 below respectively in the inventory of rare earth oxide in inventory and the rare earth chloride of butt, wherein, described rare earth chloride is sprayed 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 1
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 2-7
Method according to Comparative Examples 1 prepares catalytic cracking catalyst respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, described the first Y zeolite, described the second Y zeolite, described the 3rd Y zeolite, 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 is sprayed 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-DC7.
Table 2
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
Respectively with catalytic cracking catalyst C1-C9 and the DC1-DC7 of above-mentioned preparation, under 800 ℃, the condition of 100% water vapour aging 17 hours, be filled in afterwards in the small fixed flowing bed ACE device (available from U.S. KTI company), amount of fill is 9g separately.Then, be that 500 ℃, air speed are 16h in reaction temperature
-1, oil ratio (weight) is under 6 the condition, respectively with the catalytic mixing shown in the table 3 oil A and catalytic mixing oil B as feedstock oil, inject the fixed fluidized bed ACE device that is filled with described catalytic cracking catalyst C1-C9 and DC1-DC7 and carry 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 4 below:
Table 3
| Feedstock oil | Catalytic mixing oil A | Catalytic mixing oil B |
| Density (20 ℃), g/cm 3 | 0.9334 | 0.9263 |
| Refractive power (70 ℃) | 1.5061 | 1.5031 |
| Four components, % by weight | ||
| Saturated hydrocarbons | 55.6 | 58 |
| |
30 | 27.05 |
| Colloid | 14.4 | 14.95 |
| Asphalitine | ＜0.1 | ＜0.1 |
| Freezing point, ℃ | 34 | 33 |
| Tenor, μ g/g | ||
| Ca | 3.9 | 2.2 |
| Fe | 1.1 | 0.65 |
| Na | 0.8 | 0.6 |
| Ni | 3.1 | 3.1 |
| V | 0.5 | 0.5 |
| Element forms, % by weight | ||
| C | 86.88 | 86.69 |
| H | 11.94 | 11.91 |
| S | 0.7 | 0.71 |
| N | 0.27 | 0.38 |
| Carbon residue, % by weight | 1.77 | 1.05 |
| Basic nitrogen, μ g/g | 912 | 1411 |
Table 4
Data by table 4 can be found out, 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, can obtain higher conversion ratio, and, after basic n content in the catalytic mixing oil increases, adopt described catalytic cracking catalyst of the present invention to carry out in the process of catalytic cracking reaction, the conversion ratio fall is less, illustrates that the ability of alkali resistance nitrogen compound of described catalytic cracking catalyst of the present invention is stronger.
Claims (16)
1. catalytic cracking catalyst, this catalytic cracking catalyst contains the cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, described cracking activity constituent element contains Y zeolite, 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.
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, 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.
10. catalytic cracking catalyst according to claim 9, 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.
11. according to claim 1, the described catalytic cracking catalyst of any one in 9 and 10, wherein, gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first Y zeolite of 5-70 % by weight, the second Y zeolite of 0-55 % by weight and the 3rd Y zeolite of 0-95 % by weight, and the total content of described the second Y zeolite and described the 3rd Y zeolite is the 30-95 % by weight; Described the first Y zeolite is the DASY molecular sieve that contains rare earth; Described the second Y zeolite is the REY molecular sieve; In described the 3rd Y zeolite take the content of rare earth of rare earth oxide as the 12-16 % by weight, with P
2O
5The phosphorus content of meter is the 0.5-7 % by weight, this molecular sieve
31In the P MAS NMR spectrum, the percentage that chemical shift accounts for total peak area for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal is greater than 85%, this molecular sieve
27In the Al MAS NMR spectrum, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the percentage of total peak area greater than 20%.
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, wherein, 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) described mesoporous silica-alumina materials, clay and the binding agent that obtains in cracking activity constituent element, the step (1) mixed making beating, then carry out successively spray-drying, washing, filtration and drying, wherein, described cracking activity constituent element contains Y zeolite.
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).
16. according to claim 12 or 15 described methods, wherein, gross weight in described cracking activity constituent element, described cracking activity constituent element contains the first Y zeolite of 5-70 % by weight, the second Y zeolite of 0-55 % by weight and the 3rd Y zeolite of 0-95 % by weight, and the total content of described the second Y zeolite and described the 3rd Y zeolite is the 30-95 % by weight;
Described the first Y zeolite is the DASY molecular sieve that contains rare earth;
Described the second Y zeolite is the REY molecular sieve;
In described the 3rd Y zeolite take the content of rare earth of rare earth oxide as the 12-16 % by weight, with P
2O
5The phosphorus content of meter is the 0.5-7 % by weight, this molecular sieve
31In the P MAS NMR spectrum, the percentage that chemical shift accounts for total peak area for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal is greater than 85%, this molecular sieve
27In the Al MAS NMR spectrum, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the percentage of total peak area greater than 20%.
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| CN105195218A (en) * | 2014-06-10 | 2015-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN110871104A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Porous catalytic material and preparation method thereof |
| CN111744541A (en) * | 2020-06-23 | 2020-10-09 | 中国石油天然气集团有限公司 | Catalytic cracking catalyst containing high-silicon shape-selective molecular sieve 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 |
| JP2008173580A (en) * | 2007-01-19 | 2008-07-31 | Petroleum Energy Center | Catalytic cracking catalyst of hydrocarbon oil and catalytic cracking method of hydrocarbon oil using it |
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| JP2008173580A (en) * | 2007-01-19 | 2008-07-31 | Petroleum Energy Center | Catalytic cracking catalyst of hydrocarbon oil and catalytic cracking method of hydrocarbon oil using it |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105195218A (en) * | 2014-06-10 | 2015-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN105195218B (en) * | 2014-06-10 | 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 |
| CN110871104A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Porous catalytic material and preparation method thereof |
| CN110871104B (en) * | 2018-08-29 | 2022-10-21 | 中国石油化工股份有限公司 | Porous catalytic material and preparation method thereof |
| CN111744541A (en) * | 2020-06-23 | 2020-10-09 | 中国石油天然气集团有限公司 | Catalytic cracking catalyst containing high-silicon shape-selective molecular sieve and preparation method thereof |
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