CN101455977B - Preparation method of silicon-containing cracking catalyst - Google Patents
Preparation method of silicon-containing cracking catalyst Download PDFInfo
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Abstract
The invention provides a method for preparing a catalytic cracking catalyst. The method comprises the following steps: (1) deionized water and aluminum binder are mixed, beaten and added with acid and anticoagulant polymerization inhibitor; (2) part of silicon binder and clay are mixed and beaten; (3) molecular sieves and the deionized water are mixed and beaten; (4) serous fluids in steps (1), (2) and (3) are mixed and beaten; (5) a serous fluid obtained in a steps (4) is added with silicon binder, beaten and then added with acid; and (6) the serous fluid in step (5) is dried. The method is used for preparing the cracking catalyst containing silicon binder, can overcome the disadvantages that colloid in a method using silica sol to prepare the catalyst is easy to solidify, loses fluidity and is incapable of spray molding, and is low in preparation cost. The cracking catalyst prepared by the method has the advantages of good wear resistance, low bulk density, large pore volume, large aperture and good heavy oil cracking capability.
Description
Technical field
The present invention relates to a kind of preparation method of catalytic cracking catalyst.
Background technology
Generally speaking, the Cracking catalyst anti-wear performance that contains silica sol binder is good, and preparation cost is low.
USP3867308 discloses to adopt and has contained the method for preparing Cracking catalyst that the sodium Ludox is a binding agent, and the wear-resisting performance of catalyst of this method preparation is good, but bulk density is big, is unfavorable for fluidisation, and surface area is low, and pore volume is little, is unfavorable for the catalytic cracking of heavy oil.
USP4022714 and USP4107088 disclose catalyst and the preparation method that a kind of titanium, zirconium, iron, cerium, boron modification contain the preparation of sodium Ludox, carry out modification by these metal pair Ludox, to improve the specific surface and the cracking activity of fresh catalyst, but exist bulk density big equally, problems such as pore volume is little are not suitable for most of FCC apparatus uses of present stage.
USP5346875 discloses a kind of preparation method of fluid cracking catalyst, prepares catalyst by the isoelectric point of each component of coupling catalyst and the pH of inorganic oxide sol, and wherein inorganic oxide sol is Ludox or aluminium colloidal sol.Adopt the Ludox catalyst of the method preparation, unfavorable factor such as abrasion resistance properties is greatly improved, but exists bulk density big equally, and surface area is low, and pore volume is little.
U.S. Pat P4946814 discloses the method for improving the catalytic cracking catalyst anti-wear performance that contains silica sol binder with surfactant, spray-drying prepares catalyst to adopt Ludox, kaolin oar liquid, molecular sieve pulp and four bursts of logistics of activated alumina slurries to mix then continuously, it is binding agent that this method only adopts Ludox, and must add expensive surfactant to guarantee the anti-wear performance of catalyst.
CN1749365A discloses a kind of Cracking catalyst of using silicon bonding, it is characterized in that this catalyst is by the clay of the molecular sieve of the heavy % of 10-60, the heavy % of 0-75, with SiO
2Meter 5-40 weighs the silicon bonding of % and forms in the modified component of the heavy % of oxide 0-10, this catalyst is the method that adopts colloidal sol and gel phase combination, before shaping of catalyst, keep slurries to be in dissolved colloidal state, generate the microspheroidal gel for 50-150 ℃ by control spray-drying exhaust temperature, the reaming of wearing out again processing obtains.
CN1690169A discloses a kind of preparation method who contains the molecular sieve hydrocarbon cracking catalyzer, this method comprises aluminium colloidal sol, hydrated alumina, clay, acid, molecular sieve and water making beating is mixed, make a kind of slurries, the solid content that makes slurries is 25-40 weight %, the dry then slurries that obtain, also add a kind of Ludox when making beating, described Ludox is that average particulate diameter is the particle of 5-100 nanometer, and the particle diameter more than 80% is between 0.5-1.5 times of average particulate diameter.The catalyst that this method is prepared has big average pore diameter, and bore dia is that the middle macropore pore volume of 5-100 nanometer is bigger, has higher light oil selectivity and lower coke selectivity.
Chinese patent CN1552801A has announced a kind of catalytic cracking catalyst that contains silica sol binder and preparation method thereof, its preparation method is that Ludox, kaolin, boehmite and molecular sieve are made 2,3 or 4 bursts of logistics respectively, proportion of composing according to catalyst, each burst logistics is mixed, spray-dried, the washing, drying and other steps promptly gets catalyst again.In this method for preparing catalyst, two plume hybrid modes are: Ludox is a plume, and clay, boehmite and molecular sieve pulp are another plume; Three plume hybrid modes are: Ludox, molecular sieve respectively are a plume, the mixed serum of clay and boehmite is a plume, or Ludox, clay respectively are a plume, the mixed serum of boehmite and molecular sieve is a plume, or Ludox, boehmite slurries respectively be a plume, and the mixed serum of clay and molecular sieve is a plume; Four plume hybrid modes are: Ludox, molecular sieve pulp, clay slurry and boehmite slurries respectively are a plume.
Existing prepare in the cracking catalyst containing silicon binder process, exist colloid to condense easily, form gel, lose flowability with Ludox, thus problem that can't moulding, and prepared catalyst buildup density (heap than) is big, and surface area is low, and pore volume is low.Along with the change day by day of catalytically cracked stock is heavy, increase Cracking catalyst aperture and big mesopore pore volume become and improve optionally important means of Cracking catalyst.
Summary of the invention
The technical problem to be solved in the present invention is to overcome existing prepare the colloid that exists in the cracking catalyst containing silicon binder process with Ludox and be easy to condense, and the problem that loses flowability provides a kind of preparation method of new cracking catalyst containing silicon binder.
A kind of preparation method of catalytic cracking catalyst may further comprise the steps:
(1) deionized water and al binder are mixed, making beating adds acid, anti-freezing polymerization inhibitor, and the consumption of acid makes the pH value of slurries not be higher than 5;
(2) silicon bonding, water are mixed making beating, the 5-35 weight % that described silicon bonding consumption is a silicon bonding total amount in the catalyst with clay;
(3) molecular sieve is mixed making beating with deionized water;
(4) step (1), (2) prepared slurries are mixed, the molecular sieve pulp of step (3) is introduced in making beating then, making beating;
(5) in the resulting slurries of step (4), add silicon bonding, making beating, the 65-95 weight % that described silicon bonding consumption is a silicon bonding total amount in the catalyst adds acid then, and the consumption of acid makes the pH value of slurries not be higher than 5;
(6) with the slurry dried of step (5).
The present invention also provides a kind of catalytic cracking catalyst, it is characterized in that, described catalyst is prepared by the invention described above method.
Method for preparing catalyst of the present invention is used to prepare cracking catalyst containing silicon binder, can overcome with Ludox to prepare in the method for catalyst, and colloid condenses easily, lose flowability, thus shortcoming that can't spray shaping, preparation cost is low.The Cracking catalyst of the inventive method preparation, anti-wear performance is good, and bulk density is little, and specific area is big, the pore volume height, the aperture is big, and catalyst of the present invention is used for residual oil cracking, and heavy oil cracking ability is strong, the yield of gasoline height.For example, silica content according to the inventive method preparation is 19.5 weight %, kaolin content is 29.1 weight %, alumina content is 17.4 weight %, the DASY molecular sieve content is the catalyst of 34.0 weight %, its BET method pore volume is 0.224ml/g, heap is than being 0.69g/ml, abrasion index is 1.3%, in the preparation process, slurries are placed before spray-drying and were not lost flowability in 3 days, and according to the catalyst of the same composition of existing method preparation, BET method pore volume is 0.205ml/g, heap is than being 0.74g/ml, and abrasion index is 2.5%, and slurries are placed before spray-drying and lost flowability in 20 hours.The catalyst of the invention described above preparation mixes according to 5: 95 ratio with industrial GOR-II catalyst, aging back is on the ACE device, and mixing three heavy oil with force is raw material, in 500 ℃, agent weight of oil ratio is to react under 7.03 conditions, the heavy oil yield is 6.77 weight %, and yield of gasoline is 51.31 weight %, and conversion ratio is 79.1 weight %, and the catalyst of above-mentioned existing method preparation reacts under similarity condition, the heavy oil yield is 7.1 weight %, and yield of gasoline is 49.96 weight %, and conversion ratio is 78.6 weight %.
The specific embodiment
According to the method for the invention, weight with catalyst is benchmark, and the consumption of each component makes catalyst contain silicon bonding in silica 10-40 weight %, in aluminium oxide 10-30 weight % al binder, 10-40 weight % molecular sieve, the clay of 10-60 weight %.
According to method for preparing catalyst of the present invention, in the step (1), in aluminium oxide, the weight ratio of al binder and anti-freezing polymerization inhibitor is 1: 0.006-1: 2, be preferably 1: 0.06-1: 2.Described anti-freezing polymerization inhibitor is selected from biology, fumarate, the maleate one or more of prolonging of alkynol and they; Described alkynol is 1-acetenyl-1-cyclopentanol 1-acetenyl-1-cyclohexanol for example, and described propargyl alcohol derivative is the propoxyl group propilolic alcohol for example.
According to method for preparing catalyst of the present invention, the method for described in the step (1) deionized water and al binder being mixed, pulling an oar is a prior art, does not have specific (special) requirements; The consumption of described acid makes the pH value that adds sour rear slurry be 2-4, and described acid is one or more in the acid of using always in the al binder acidifying in the existing Cracking catalyst preparation process, is preferably hydrochloric acid.It is 20-50 weight % that the consumption of preferred each component makes the solid content of resulting slurries.
According to method for preparing catalyst of the present invention, described silicon bonding is introduced in two steps, and the silicon bonding amount of introducing in the step (2) is the 5-35% of total introducing amount, and all the other are introduced in step (5).Described silicon bonding is one or more in water dissolvable silicate, the Ludox, is preferably waterglass.The modulus of preferred water glass is 1.5-3.5, SiO in the water glass solution
2Content be 5-50 weight %, more preferably the modulus of waterglass is 2.5-3.5, SiO in the water glass solution
2Content be 5-30 weight %.To make the solid content of resulting slurries be 20-50 weight % to the consumption of each component in the preferred steps (2).
According to method for preparing catalyst of the present invention, the described molecular sieve making beating of step (3) is compared with the method for having now does not have specific (special) requirements, and the solid content of preferred resulting molecular sieve pulp is 20-50 weight %.
According to method for preparing catalyst of the present invention, the consumption of the described acid of step (5) makes the pH value of slurries be 2-3, and described acid is one or more of inorganic acid, and described inorganic acid is phosphoric acid, nitric acid, hydrochloric acid for example.
According to method for preparing catalyst of the present invention, in the step (3), molecular sieve is with after water mixes, and beating time was not less than 15 minutes, preferred 15-60 minute.In the step (4), after three kinds of slurries mixing, beating time was not less than 15 minutes, preferred 15-60 minute.After introducing silicon bonding in the step (5), making beating was not less than 20 minutes, preferably pulled an oar 20-45 minute.
According to method for preparing catalyst of the present invention, described molecular screening is from being commonly used for the zeolite molecular sieve of catalytic cracking catalyst active component and in the non-zeolite molecular sieve one or more, and described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujasite, L zeolite, Beta zeolite, omega zeolite, modenite, the ZSM-18 zeolite one or more, the particularly overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, in the Beta zeolite one or more.Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, for example has in the zeolite with MFI structure (the disclosed phosphorous zeolite with MFI structure of ZSM-5 zeolite, CN 94181A for example phosphorous and/or rare earth), ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite of the zeolite (for example ZSM-5 zeolite) of MFI structure, phosphorous and/or rare earth one or more.Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by other element such as phosphorus, titanium, gallium, the molecular sieve of one or more replacements in the germanium comprises silicate with Different Silicon aluminum ratio (metal silicate metallosilicate for example, titan silicate titanosilicate), metal aluminate metalloaluminates (for example germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphate metalloaluminophosphates, the silicoaluminophosphate metal integrated silicoaluminophosphates (MeAPSO) of metal combination, silicoaluminophosphate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.Preferred non-zeolite molecular sieve is one or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve.
Molecular sieve of the present invention is one or more in the zeolite with MFI structure of overstable gamma zeolite, Beta zeolite, the zeolite with MFI structure, the phosphorous and/or rare earth of y-type zeolite, overstable gamma zeolite, the phosphorous and/or rare earth of y-type zeolite, phosphorous and/or rare earth more preferably.
According to method for preparing catalyst of the present invention, described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
According to method for preparing catalyst of the present invention, described al binder is selected from boehmite, have a diaspore structure hydrated alumina, have gibbsite structure hydrated alumina, have in bayerite structure hydrated alumina, gama-alumina, η-aluminium oxide, θ-aluminium oxide, the χ-aluminium oxide one or more.Be preferably boehmite.
According to method for preparing catalyst of the present invention, described deionized water is decationized Y sieve water, remove the water of negative and positive, decationized Y sieve water in ammonia and resulting water.
According to method for preparing catalyst of the present invention, also comprise the step of introducing rare earth oxide.Described rare earth oxide can be introduced in step (1), (2), (3), (4) or (5) arbitrary step.Described rare earth oxide is introduced by the solution of introducing compounds containing rare earth in the process of Preparation of Catalyst, preferably introduces the solution of rare earth compound in the slurries of step (5).Described rare earth compound is chloride, nitrate or the lanthanide series metal chloride of mishmetal, in the nitrate one or more.With the catalyst weight is benchmark, and the content of described catalyst middle rare earth oxide is 0.5-2 weight %.
According to method for preparing catalyst of the present invention, also can comprise the step of introducing additive, described additive is the oxide of P, Fe, Co, Ni, Mg for example, is benchmark with the weight of catalyst, and the introducing amount of described additive is no more than 20 weight %.Described additive can be introduced in any step of Preparation of Catalyst, for example introduces in step (4) or (5).
According to method for preparing catalyst of the present invention, dryly described in the step (6) be drying means commonly used in the existing catalytic cracking catalyst preparation, spray-drying for example, the present invention does not have specific (special) requirements.
According to method for preparing catalyst of the present invention, also can be to dried catalyst roasting.Roasting condition is a roasting condition habitual in the catalytic cracking catalyst preparation process, and the present invention does not have specific (special) requirements.
Following example will give further instruction to the present invention, but not thereby limiting the invention.
In each example and Comparative Examples, V
BETThe heap that adopts RIPP151-90 methods analyst, catalyst is than adopting the RIPP31-90 methods analyst, AI (abrasion index) adopts the RIPP29-90 methods analyst, referring to " petrochemical industry analytical method (RIPP experimental technique), volumes such as Yang Cuiding, Science Press, nineteen ninety publishes.
Example 1
With 40Kg decationized Y sieve water with 8.64Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63 weight %) making beating, with hydrochloric acid (technical grade, concentration 31 weight %, back embodiment is identical with the used hydrochloric acid of Comparative Examples) its pH value is transferred to 3, add 1-acetenyl-1-cyclopentanol 4.0Kg then and stir.(silica content 26.9 weight %, modulus 3.1 descend together) pull an oar 44.44Kg halloysite slurries (Suzhou china clay company industrial products, solid content 45 weight %) 15 minutes with the 2.72Kg water glass solution.Above-mentioned two kinds of slurries are mixed, add 25kg water, add ZSM-5 (silica alumina ratio 50, catalyst Shandong branch company of China Petrochemical Industry produce) molecular sieve pulp 32.92kg (concentration of slurry is 37.97 weight %) again, pulled an oar 15 minutes, add water glass solution 42.63kg (silica content 26.9 weight %) again, pulled an oar 20 minutes, under agitation add hydrochloric acid then, when the pH value is 2.3, stop to add hydrochloric acid, add compound re chloride 1Kg (with RE
2O
3Meter concentration is 300g/kg, wherein La
2O
3Account for 65 weight %, Ce
2O
3Account for 35 weight %), stirred 5 minutes, spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample A.The rerum natura of A sees Table 1.In the present embodiment, the slurries before the spray-drying were placed 72 hours, did not lose flowability.
Example 2
With 11.9Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) making beating, its pH value is transferred to 2.5 with 50Kg decationized Y sieve water, add 1-acetenyl-1-cyclohexanol 970g then and stir with hydrochloric acid.With 6.49Kg water glass solution (silica content 26.9 weight %) 44.44Kg halloysite slurries (Suzhou china clay company industrial products, solid content 45 weight %) were pulled an oar 15 minutes.Above-mentioned two kinds of slurries are mixed, add water 22kg, (concentration of slurry is 34.65% to add molecular sieve pulp 19.08kg again, wherein ZRP molecular sieve (silica alumina ratio 55, catalyst Shandong branch company of China Petrochemical Industry produce) accounts for 92%, (catalyst Shandong branch company of China Petrochemical Industry produces beta-molecular sieve, silica alumina ratio 30) accounts for 8%), stirred 15 minutes, add water glass solution 22.56kg (silica content 26.9 weight %) again, stir, stir adding phosphoric acid (concentration is 55 weight %) down, when the pH value is 2.1, stop to add phosphoric acid, add compound re chloride 3.0kg (with RE
2O
3Meter concentration is 300g/kg, wherein La
2O
3Account for 65 weight %, Ce
2O
3Account for 35 weight %), stirred 5 minutes.Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample B.The rerum natura of B sees Table 1.In the present embodiment, the slurries before the spray-drying were placed 72 hours, did not lose flowability.
Example 3
With 15.87Kg boehmite (Shandong Aluminum Plant's industrial products, solid content 63m%) making beating, its pH value is transferred to 3.5 with 70Kg decationized Y sieve water, add maleate 7Kg then and stir with hydrochloric acid.With 8.45Kg water glass solution (silica content 26.9 weight %) 44.44Kg halloysite slurries (Suzhou china clay company industrial products, solid content 45 weight %) were pulled an oar 15 minutes.Above-mentioned two kinds of slurries are mixed, add water 10kg, adding molecular sieve pulp 15.41kg[concentration of slurry again is 39.57 weight %, ZSP-2 molecular sieve (silica alumina ratio 50 wherein, catalyst Shandong branch company of China Petrochemical Industry produces) account for 96%, beta-molecular sieve (with embodiment 2) accounts for 4%] stirred 15 minutes, add water glass solution 15.70kg (silica content 26.9 weight %) again, stir, stir and add sulfuric acid (concentration is 65 weight %) down, when the pH value is 2.5, stop to add sulfuric acid, add compound re chloride 2.5kg (with RE
2O
3Meter concentration is 300g/kg, wherein La
2O
3Account for 65 weight %, Ce
2O
3Account for 35 weight %), stirred 5 minutes.Spray drying forming, the flush away Na ion that dissociates is drying to obtain catalyst sample C.The rerum natura of C sees Table 1.In the present embodiment, the slurries before the spray-drying were placed 72 hours, did not lose flowability.
Example 4
Get 580 gram kaolin (Suzhou kaolin company product, solid content 80 weight %), add deionized water and 111g water glass solution (silica content 26.9 weight %), making beating, slurry solid content is 30 weight %; Contain Al
2O
3(Shandong Aluminum Plant produces the boehmite of 233 grams, Al
2O
3Content 33 weight %) and deionized water mix making beating 1 hour, add then and contain 24 gram Al
2O
3Aluminium colloidal sol (catalysis Shandong branch company of China Petrochemical Industry produce, alumina content 22 weight %), making beating, slurry solid content is 32 weight %, adds hydrochloric acid its pH value is transferred to 3.5, adds maleate 58g then and stirs; 1695 gram molecules sieve (the molecular sieve industry trade mark is DASY0.0, and the Shandong catalyst plant is produced) is mixed with water, pulled an oar 2 hours, grind, getting solid content is the molecular sieve pulp of 32 weight %; Then above-mentioned three kinds of slurries are mixed, making beating, add water glass solution 1040g (silica solid content 26.9 weight %), stir, stir adding sulfuric acid (concentration is 65 weight %) down, when being 2.5, the pH value stops to add sulfuric acid, stir, spray-drying under 180 ℃ temperature is not detected to there being sodium ion with the washing of sulphur aqueous ammonium, in 150 ℃ of oven dry, obtain catalyst D again.In the present embodiment, the slurries before the spray-drying were placed 72 hours, did not lose flowability.
Comparative Examples 1
The explanation of this Comparative Examples prepares catalytic cracking catalyst according to the method for CN1552801A.
Ludox preparation: water glass solution and 1 liter of free acid that to prepare 2 liters of silica concentrations be 155g/l are 148g/l, Al
2O
3Content is the acidified aluminum sulfate solution of 20g/l, and above-mentioned two kinds of solution enter the flash mixer reaction simultaneously.The preparation of the mixed serum of kaolin, boehmite and molecular sieve: get 580 gram kaolin (Suzhou kaolin company product, solid content 80 weight %) respectively, contain 24 gram Al
2O
3Aluminium colloidal sol (catalysis Shandong branch company of China Petrochemical Industry produce, alumina content 22 weight %), the ground molecular sieve content of 1695 grams is the molecular sieve pulp (the molecular sieve industry trade mark is DASY0.0, and the Shandong catalyst plant is produced) of 32 weight %, contains Al
2O
3(Shandong Aluminum Plant produces the boehmite of 233 grams, Al
2O
3Content 33 weight %) and deionized water mix making beating 2 hours, adding 26 ml concns then is hydrochloric acid (acid/Al of 31 weight %
2O
3Weight ratio is 0.04) peptization, it is standby after 30 minutes to continue making beating, and the solid content of mixed serum is 42 weight %.
Preparation of catalysts: in the mixing kettle that stirs fast with the Ludox of above-mentioned preparation and above the kaolin for preparing, the mixed serum of boehmite and molecular sieve mixes and obtains the catalyst precursor slurries, then under 180 ℃ temperature with the slurries spray drying forming that obtains, obtaining diameter is the 20-120 micron, silica content is 19.5 weight %, kaolin content is 29.1 weight %, alumina content is 17.4 weight %, molecular sieve content is the solid particle of 34.0 weight %, be not detected to there being sodium ion with the washing of sulphur aqueous ammonium, 150 ℃ of oven dry, obtain catalyst DB2, testing its abrasion index is 2.5.Slurries before the spray-drying were placed 20 hours, lost flowability.
With catalyst A, B, C, D, DB2 is that GOR-II Industrial Catalysis Cracking catalyst (catalyst Shandong branch company of China Petrochemical Industry product) is mixed with trade names respectively, obtain catalyst A A, BB, CC, DD, DB-2, A, B, C, D or DB2 catalyst account for 5 weight % in wherein resulting each catalyst, and GOR-II accounts for 95 weight %.
Embodiment 5～8
On ACE (fixed fluidized bed) device, mixing three oil (character sees Table 2) with force is that raw material is estimated catalyst sample AA, BB, CC, DD respectively, and the catalyst loading amount is 25 grams, and reaction temperature is 500 ℃, and agent weight of oil ratio is 7.03.Before the reaction, catalyst sample is through 800 ℃, 100% steam treatment 17 hours.The results are shown in Table 3.
Comparative Examples 2～3
Method according to embodiment 5 is estimated DB-2, GOR-II catalyst.The results are shown in Table 3 by table 3 as seen, catalyst of the present invention is used for catalytic cracking, has higher heavy oil cracking activity.
Table 1
| The embodiment numbering | Comparative Examples 1 | 1 | 2 | 3 | 4 |
| The catalyst numbering | DB2 | A | B | C | D |
| AI，％ | 2.5 | 1.5 | 0.9 | 1.8 | 1.3 |
| The heap ratio, g/ml | 0.74 | 0.68 | 0.62 | 0.70 | 0.69 |
| V BET，ml/g | 0.205 | 0.238 | 0.214 | 0.256 | 0.224 |
Table 2
| Density (20 ℃), g/cm 3 | 0.9006 | |
| Kinematic viscosity (100 ℃), mm 2/s | 11.0 | |
| Carbon residue, w% | 3.14 | |
| Density (20 ℃), g/cm 3 | 0.9006 | |
| Element is formed, w% | C | 85.7 |
| H | 12.8 | |
| N | 038 | |
| S | 0.77 | |
| Group composition, w% | Saturated hydrocarbons | 57.5 |
| Aromatic hydrocarbons | 24.5 | |
| Colloid | 16.9 | |
| Asphalitine | 1.1 | |
| Tenor, ppm by weight | Ni | 5.0 |
| V | 0.8 | |
| Boiling range, ℃ | IBP | - |
| 5％ | 217 | |
| 40％ | 396 | |
| 70％ | 456 | |
| Characterization factor | 12.0 | |
Table 3
| The embodiment numbering | 5 | 6 | 7 | 8 | Comparative Examples 2 | Comparative Examples 3 |
| The catalyst numbering | AA | BB | CC | DD | DB-2 | GOR-II |
| Dry gas, weight % | 1.64 | 1.63 | 1.68 | 1.71 | 1.61 | 1.42 |
| Liquefied gas, weight % | 18.91 | 19.08 | 19.26 | 19.17 | 18.02 | 16.15 |
| The embodiment numbering | 5 | 6 | 7 | 8 | Comparative Examples 2 | Comparative Examples 3 |
| Propane | 1.06 | 1.10 | 1.15 | 1.22 | 1.26 | 1.08 |
| Propylene | 5.39 | 5.76 | 6.42 | 6.44 | 6.56 | 3.84 |
| Normal butane | 0.87 | 0.88 | 0.88 | 0.90 | 0.71 | 0.85 |
| Iso-butane | 5.11 | 5.42 | 5.51 | 5.31 | 5.12 | 4.96 |
| Butene-1 | 1.08 | 1.10 | 1.03 | 1.07 | 1.11 | 1.08 |
| Isobutene | 1.51 | 1.13 | 1.35 | 1.33 | 1.57 | 1.20 |
| Suitable-butene-2 | 1.25 | 1.16 | 1.14 | 1.20 | 1.34 | 1.22 |
| Instead-butene-2 | 1.55 | 1.47 | 1.43 | 1.53 | 1.52 | 1.92 |
| Gasoline, weight % | 50.12 | 50.39 | 50.26 | 51.31 | 49.96 | 48.53 |
| Diesel oil, weight % | 13.45 | 13.36 | 13.19 | 13.52 | 14.30 | 15.67 |
| Heavy oil, weight % | 6.98 | 7.0 | 6.94 | 6.77 | 7.1 | 9.64 |
| Coke, weight % | 8.9 | 8.53 | 8.67 | 7.52 | 8.2 | 8.59 |
| Conversion ratio, weight % | 79.57 | 79.63 | 79.87 | 79.71 | 78.60 | 74.69 |
Claims (8)
1. the preparation method of a catalytic cracking catalyst may further comprise the steps:
(1) deionized water and al binder are mixed, making beating adds acid, anti-freezing polymerization inhibitor, and the consumption of acid makes the pH value of slurries not be higher than 5, and described anti-freezing polymerization inhibitor is selected from one or more in alkynol, fumarate, the maleate;
(2) silicon bonding is mixed making beating, the 5-35 weight % that described silicon bonding consumption is a silicon bonding total amount in the catalyst with clay;
(3) molecular sieve is mixed making beating with deionized water;
(4) step (1), (2) prepared slurries are mixed, the molecular sieve pulp of step (3) is introduced in making beating then, making beating;
(5) in the resulting slurries of step (4), add silicon bonding, making beating, the 65-95 weight % that described silicon bonding consumption is a silicon bonding total amount in the catalyst adds acid then, and the consumption of acid makes the pH value of slurries not be higher than 5;
(6) with the slurry dried of step (5).
2. in accordance with the method for claim 1, it is characterized in that, weight with catalyst is benchmark, the consumption of each component makes catalyst contain silicon bonding in silica 10-40 weight %, in aluminium oxide 10-30 weight % al binder, 10-40 weight % molecular sieve, the clay of 10-60 weight %.
3. in accordance with the method for claim 1, it is characterized in that in aluminium oxide, the weight ratio of al binder and anti-freezing polymerization inhibitor is 1: 0.006-1: 2, described anti-freezing polymerization inhibitor is selected from one or more in alkynol, fumarate, the maleate.
4. in accordance with the method for claim 1, it is characterized in that the consumption of the described acid of step (1) makes the pH value of slurries be 2-4, the consumption of the described acid of step (5) makes the pH value of slurries be 2-3.
5. in accordance with the method for claim 1, it is characterized in that described silicon bonding is waterglass and/or Ludox.
6. in accordance with the method for claim 1, it is characterized in that described al binder is boehmite, have a diaspore structure hydrated alumina, have gibbsite structure hydrated alumina, have in bayerite structure hydrated alumina, gama-alumina, η-aluminium oxide, θ-aluminium oxide, the χ-aluminium oxide one or more.
7. in accordance with the method for claim 1, it is characterized in that, also comprise the step of introducing rare earth oxide, is benchmark with the weight of catalyst, and the introducing amount of described rare earth oxide is 0.5～2 weight %.
8. a catalytic cracking catalyst is characterized in that, described catalyst is according to each described method preparation of claim 1-7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082093A (en) * | 1992-08-14 | 1994-02-16 | 中国石油化工总公司 | Improve the auxiliary agent of gasoline octane rating and increase by third, butylene productive rate |
| CN1417297A (en) * | 2002-11-27 | 2003-05-14 | 吉林市京泰化工有限责任公司 | RE-containing Si-base partially-synthesized hydrocarbon converting catalyst |
| CN1552801A (en) * | 2003-06-02 | 2004-12-08 | 中国石油化工集团公司长岭炼油化工有 | Catalytic cracking catalyst and preparing method thereof |
| CN1727442A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst for petroleum hydrocarbon, and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082093A (en) * | 1992-08-14 | 1994-02-16 | 中国石油化工总公司 | Improve the auxiliary agent of gasoline octane rating and increase by third, butylene productive rate |
| CN1417297A (en) * | 2002-11-27 | 2003-05-14 | 吉林市京泰化工有限责任公司 | RE-containing Si-base partially-synthesized hydrocarbon converting catalyst |
| CN1552801A (en) * | 2003-06-02 | 2004-12-08 | 中国石油化工集团公司长岭炼油化工有 | Catalytic cracking catalyst and preparing method thereof |
| CN1727442A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst for petroleum hydrocarbon, and preparation method |
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