CN1042558A - The cracking catalyst that contains new-type high silicon Y zeolite - Google Patents
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Abstract
The invention discloses a kind of fluidized catalytic cracking catalyst that contains the new-type high silicon zeolite, wherein contained new-type high silicon zeolite makes through chemical dealuminization and two kinds of process alternate treatment of hydrothermal treatment consists y-type zeolite, treatment condition are shorter than using easy row of wherein a kind of more mitigation and time in the prior art separately, expense is low, and handiness is big.Product degree of crystallinity height, sodium content is low, heat and good hydrothermal stability, selectivity is strong, is suitable for handling each petroleum-like hydrocarbon by it catalyzer that makes and comprises mink cell focus or residual oil, and performance is better than similar comparative catalyst.
Description
The present invention relates to contain the fluidized catalytic cracking catalyst of new-type high silicon Y zeolite and obtain contained zeolite and prepare the method for catalyzer and this catalyzer produce application in the stop bracket gasoline at the fluid catalytic cracking hydrocarbon feed with it.
With fluid catalytic cracking processing hydrocarbon feed acquisition high yield, stop bracket gasoline is the important process in the petroleum refining industry, its key is the performance of catalyst activity component, promptly require contained high-silicon Y-Zeolite can keep crystalline structure intact, have very high heat and hydrothermal stability, acid strong and sour density is low.In order to obtain to have the supersiliceous zeolite of described performance, normally the NaY zeolite with synthetic carries out suitable processing treatment, and purpose is the aluminium content that reduces in the former zeolite, reduce lattice constant, improve the silica alumina ratio of zeolite framework, thereby reduce sour density, improve thermostability and hydrothermal stability.Treatment process for this purpose has in prior art: hydrothermal dealumination and chemical dealuminization two big classes, the former is in the presence of water vapor, high-temperature roasting NH
4Y zeolite makes high-silicon Y-Zeolite, is referred to as overstable gamma zeolite (USY) and (consults US, 3,293,192; 4,036,739); The latter uses silicofluoride, for example ammonium silicofluoride or other fluorine-containing salt, and Neutral ammonium fluoride for example, ammonium borofluoride is removed NH as dealumination agent
4Aluminium in Y or the NaY zeolite framework makes silicon move in the skeleton on the room behind the dealuminzation simultaneously, be referred to as skeleton rich silicon Y zeolite (FSEY) (consult US, 4,503,023, (1985); NPRA Annual Meeting 1986, AM-86-30).Perhaps make dealumination agent with ethylenediamine tetraacetic acid (EDTA) etc., the supersiliceous zeolite that makes claims sealumination modified Y zeolite (DAY) (consult US, 3,442,795(1969)).USY has suppressed hydrogen transfer reactions owing to reduced sour density, thereby can produce stop bracket gasoline, and can be used for processing heavy oil, but in its preparation process, the speed of zeolite framework dealuminzation and silicon migration is difficult to coupling, make the room that produces in the framework dealumination process not go to occupy by Siliciumatom in time, thereby influence the stability of skeleton, even in the room more for a long time, can produce the skeleton structure avalanche, make degree of crystallinity impaired, the active reduction.In addition, stabilization reactions in the treating processes is carried out in solid phase, the aluminium of deviating from from skeleton is still stayed in the cage structure of zeolite, the aluminium of this non-skeleton " fragment " can make nonselective scission reaction increase, thereby the productive rate that reduces gasoline (is consulted Pellet, R.J etc., J.Catal, 114,71-89(1988)).European patent prospectus EP 82111(1983) with Chinese patent prospectus CN, 85108330A(1987) discloses the novel method for preparing high-silicon Y-Zeolite, makes the supersiliceous zeolite of commodity LZ-210 by name, promptly handles NH with ammonium fluosilicate solution
4Y or NaY zeolite, aluminium on the zeolite framework is entered solution by the fluorine complexing, and the silicon in the solution is transferred on the empty position that stays behind the dealuminzation subsequently, dealuminzation that this solid-liquid is alternate and Silicon-rich process are easier to the condition that finds aluminium and the two transport velocity of silicon to be complementary, make the skeleton defective of the LZ-210 zeolite that makes less, crystallization reservation degree height does not contain framework aluminum " fragment ".The silica alumina ratio of skeleton can be regulated arbitrarily, and sodium content is also lower, its heat and hydrothermal stability height, by the catalyzer that makes as active ingredient compare with the similar catalyst that contains USY, activity is higher, selectivity is better, ability with preventing from heavy metal pollution can be used for handling mink cell focus or residual oil.
Above-mentioned USY zeolite working condition harshness, technology is numerous and diverse, the technology that the silicofluoride dealuminzation prepares supersiliceous zeolite on industrial production also existence condition control require sternly, technical process is long, problems such as production cost height have limited its widespread use.Need develop novel fluidized catalytic cracking catalyst in order to overcome above-mentioned unfavorable factor, the invention provides a kind of method that chemical dealuminization process and hydrothermal treatment consists process combine that is used alternatingly, can use more cheap feedstock production new-type high silicon Y zeolite and prepare fluidized catalytic cracking catalyst comparing under the demulcent operational condition with it.
The new-type high silicon Y zeolite of the present invention preparation shown in formula I or formula II, is to be combined and the method that is used alternatingly is handled y-type zeolite and made by chemical dealuminization process and hydrothermal treatment consists process; Again by be mixed and made into fluidized catalytic cracking catalyst with matrix, can be used for handling distillate or residual oil.
Method shown in the formula I claims B method, and the formula II method claims C method.Wherein related chemical dealuminization process is under the effect of complexing agent, and the aluminium of deviating from skeleton also can be deviate from the aluminium of non-skeleton.Carry out hydrothermal treatment consists is carried out silicon in solid phase migration subsequently, make Siliciumatom occupy the room that stays behind the dealuminzation, reach the stabilization of structure, also follow hydrothermal dealumination to a certain degree herein in the reason process.As mentioned above, hocket chemical dealuminization and hydrothermal treatment consists, the degree of depth of may command dealuminzation makes the high-silicon Y-Zeolite of required silica alumina ratio, because it has FSEY and USY concurrently, so be referred to as new-type high silicon Y zeolite (NHSY).Wherein the number of times that is used alternatingly of two kinds of processes shown in the formula II is decided by the requirement to supersiliceous zeolite.
The used dealuminzation complexing agent of chemical dealuminization process of the present invention comprises: organic acid, for example can select ethylenediamine tetraacetic acid (EDTA) for use, oxalic acid, sulphosalicylic acid etc.; The organic alcohol amine class for example can be selected trolamine etc. for use; Organic and mineral acid salt, for example optional ammonium oxalate, Neutral ammonium fluoride, ammonium silicofluoride, ammonium borofluoride etc.; The mixture of the above-mentioned complexing agent of also optional usefulness, each time chemical dealuminization can be selected complexing agent identical or inequality for use.The consumption of complexing agent can calculate by stoichiometry according to the dealuminzation degree of zeolite, and pre-dealuminzation degree is determined according to the required silica alumina ratio of product.The dealuminzation condition is to guarantee that zeolite framework is even, slowly dealuminzation is a principle.The general 1-20%(weight that adopts) complexing agent aqueous solution, the most handy 5-10% solution; Reaction times 1-6 hour, preferably 2-4 hour; Temperature of reaction 25-100 ℃, preferably 50-95 ℃.The condition of hydrothermal treatment consists is shorter than mild condition and the time of system USY, and general treatment temp is 400-700 ℃, and preferably 500-600 ℃ was carried out 1-3 hour; Water concentration in the atmosphere is decided according to the needed hydrothermal dealumination degree of depth, moisture 20-100%(volume in the general atmosphere), also can be zeolite self water vapor that contains 30-50% water.
The used zeolite raw material of the present invention is a y-type zeolite, its silica alumina ratio (SiO
2/ Al
2O
3) greater than 4.0, more preferably greater than 4.5.The characteristic spectral line that the supersiliceous zeolite that makes still has faujusite (Faujusite) structure through X-ray diffraction analysis, just spacing (d
) value diminishes the SiO of product with the raising of product silica alumina ratio
2/ Al
2O
3Be controlled at 6-40 than generally, be preferably in 8-20, sodium oxide content is less than 1.0%, and preferably less than 0.5%, relative crystallinity is greater than 80%, more preferably greater than 90%.
Used matrix is an inorganic oxide in the Preparation of Catalyst of the present invention, for example can select aluminium oxide-silicon oxide, silica gel or silicon solution for use, aluminium glue or activated alumina, natural clay or their mixture etc.The mixture that is formed by two or more oxide compounds must have certain pore structure and catalytic activity.The levigated active ingredient mixed with matrix make fluidized catalytic cracking catalyst according to a conventional method, wherein can contain active ingredient 10-50%(weight), preferably contain 15-30%, this catalyzer is in the device of fluid catalytic cracking, operational condition and stock oil routinely, comprise the contact of distillate or residual oil, can produce stop bracket gasoline.
Its principal character of the supersiliceous zeolite that the present invention makes is: 1. the aluminium room in the skeleton structure of zeolite is few; 2. the aluminium distribution uniform of zeolite surfaces externally and internally; 3. non-framework aluminum " fragment " amount that is present in the skeleton structure hole can be controlled arbitrarily; 4. zeolite has flourishing secondary pore structure; 5. the sodium content of zeolite is low; 6. the silica alumina ratio of zeolite framework or lattice constant are easier to control.These characteristics make described zeolite that very high thermostability be arranged, hydrothermal stability and catalytic activity and highly selective.The fluidized catalytic cracking catalyst that makes with this zeolite has high reactivity and excellent selectivity.See Table 1-7 and Fig. 1-7.
Aluminium room in the skeleton structure of zeolite of the present invention characterizes with the defect structure factor Z, can use U.S. Pat, and 4,503,023(1985) the middle method of introducing is measured, and promptly the test sample product are at the infrared spectra 3710Cm in hydroxyl district
-1The back of the body at the bottom of absorbancy; The zeolite surface silica alumina ratio can be measured with the x-ray photoelectron power spectrum; Aluminium in the zeolite framework hole " fragment " is available
27Al MAS-NMR measures, and easier method is to measure hydroxyl district 3600Cm with method of the present invention
-1Infrared absorption band (as Fig. 1); The secondary pore structure of zeolite can be adsorbed bed thickness method mensuration with cryogenic nitrogen; Zeolite lattice constant a.X-ray diffraction method with routine is measured, and makes internal standard substance with silica flour, measures near 20 diffraction angle that equal 54 ° and 58.3 °; The degree of crystallinity of the intact degree of crystallization of zeolites with respect to initial NaY, promptly relative crystallinity is represented, concrete grammar is, with X-ray diffraction method test sample product and initial NaY in (331), (511,333), (440), (533), (642), (822,660), (555,751), the halfwidth at the diffraction peak height of (644) locating and (533) peak calculates relative crystallinity (Xi) by following formula;
Xi＝I
iW
i/I
RW
R
I represents testing sample, and R represents initial NaY, and I is the high sums of eight peak-to-peaks, and W is (533) peak width, and used testing sample is all handled through the sodium chloride solution exchange.
The stability of the high-silicon Y-Zeolite of table 1 different methods preparation relatively
Before steam is handled
After steam is handled
Sample system Na
2O Xi a
0Structural breakdown temperature Xi a
0
The heavy % % of Preparation Method 
℃ %
Silicofluoric acid 0.65 92 21.45 1,086 88 24.28
Ammonium dealuminzation method
The present invention 0.24 97 24.48 1,071 92 24.28
The B method
The present invention 0.33 92 24.44 1,056 92 24.26
The C method
Hydro-thermal takes off-93 24.45 1,002 80 24.19
The aluminium method
Annotate: the steam treatment condition: 800 ℃ of 100% steam 3 hours
The secondary pore texture ratio of the high-silicon Y-Zeolite of table 2 different methods preparation
Sample system a
0Surface-area m
2/ g micro pore volume
Preparation Method
S
AlwaysS
InS
GreatlyMl/g
Silicofluoric acid 24.45 727 12 27 0.251
Ammonium dealuminzation method
The present invention 24.47 794 53 78 0.244
The B method
The present invention 24.44 854 133 34 0.254
The C method
Hydro-thermal takes off 24.52 759 83 7 0.253
The aluminium method
* S
Always-total surface area, S
In-mesopore (40-200
) surface-area, S
Greatly-macropore (＞200
) surface-area
The surfaces of aluminum of the high-silicon Y-Zeolite of table 3 different methods preparation distributes relatively
Sample preparation methods a
0 Si/Al (I) * Si/Al (II)
Ammonium silicofluoride dealuminzation method 24.471 5.86 22.0
The inventive method 24.415 6.80 11.2
Hydrothermal dealumination method 24.482 4.73 1.27
* Si/Al(I)-silica alumina ratio measured with chemical analysis
The Si/Al(II)-silica alumina ratio measured with the x-ray photoelectron power spectrum
Table 4 catalyzer F-A evaluation result
Temperature of reaction, ℃ 480 490 500 510
WHSV 16.04 15.90 15.71 16.17
C/O is than 3.00 3.41 3.77 4.03
H
2+ C
1+ C
2, heavy % 0.67 0.90 1.10 1.40
C
3+ C
4, heavy % 18.2 21.6 23.6 25.6
Gasoline, heavy % 46.3 49.7 50.4 50.2
Diesel oil, heavy % 15.9 14.4 13.7 11.4
Heavy oil, heavy % 17.5 11.6 9.3 9.1
Coke, heavy % 1.5 1.8 2.0 2.2
Transformation efficiency, heavy % 82.5 88.3 90.7 91.1
Octane value (chromatography) 91.4 92.2 91.0
Gasoline selective, % 56.1 56.3 55.6 55.1
The lightweight oil selectivity, % 75.4 72.6 70.7 67.6
Coke selectivity, % 1.82 2.04 2.21 2.41
The dry gas selectivity, % 0.81 1.02 1.21 1.54
C
3+ C
4Selectivity, % 22.1 24.5 26.0 28.1
Table 5 catalyzer F-B evaluation result
Temperature of reaction, ℃ 470 480 490 500 510
WHSV 19.86 16.15 15.85 16.01 15.96
C/O is than 3.01 3.00 3.39 3.74 4.02
H
2+ C
1+ C
2, heavy % 0.80 1.00 1.20 1.30 1.90
C
3+ C
4, heavy % 18.1 20.0 24.1 25.6 28.7
Gasoline, heavy % 51.1 51.9 50.1 50.3 48.8
Diesel oil, heavy % 15.4 14.5 14.2 12.3 12.6
Heavy oil, heavy % 12.6 10.4 8.5 8.4 5.3
Coke, heavy % 2.0 2.1 2.3 2.2 2.9
Transformation efficiency, heavy % 87.4 89.6 91.5 91.6 94.7
Octane value (chromatography) 91.3 91.3 91.6 93.8
Gasoline selective, % 58.5 57.9 54.8 54.9 51.5
The lightweight oil selectivity, % 76.1 74.1 70.3 68.3 64.8
Coke selectivity, % 2.29 2.34 2.51 2.40 3.06
The dry gas selectivity, % 0.92 1.12 1.31 1.42 2.01
C
3+ C
4Selectivity, % 20.7 22.3 26.3 27.9 30.3
Table 6 catalyzer F-C evaluation result
Temperature of reaction, ℃ 470 480 490 500 510
WHSV 21.60 16.08 15.09 15.17 16.35
C/O is than 2.98 3.00 3.41 3.75 4.07
H
2+ C
1+ C
2, heavy % 0.8 1.0 1.3 1.5 2.0
C
3+ C
4, heavy % 18.4 20.7 24.4 27.4 29.8
Gasoline, heavy % 51.8 53.1 53.1 51.4 48.7
Diesel oil, heavy % 16.2 15.0 11.9 11.2 10.5
Heavy oil, heavy % 10.8 1.9 6.8 6.1 6.0
Coke, heavy % 2.0 2.2 2.5 2.4 3.1
Transformation efficiency, heavy % 89.2 92.1 93.2 93.9 94.6
Octane value (chromatography) 91.6 91.6 92.2
Gasoline selective, % 58.1 57.7 57.0 54.7 51.5
The lightweight oil selectivity, % 76.2 73.9 69.7 66.7 62.6
Coke selectivity, % 2.24 2.39 2.68 2.56 3.28
The dry gas selectivity, % 0.90 1.09 1.39 1.60 2.11
C
3+ C
4Selectivity, % 20.6 22.5 26.2 29.2 31.5
Table 7 catalyzer F-O evaluation result
Temperature of reaction, ℃ 480 490 500 510 520
WHSV 15.44 16.07 15.89 15.69 14.29
C/O is than 2.99 3.39 3.75 4.05 4.50
H
2+ C
1+ C
2, heavy % 0.70 1.00 1.32 1.30 1.64
C
3+ C
4, heavy % 16.7 20.2 22.9 24.2 26.9
Gasoline, heavy % 48.0 51.1 49.4 49.9 47.8
Diesel oil, heavy % 17.6 14.6 14.7 12.3 14.3
Heavy oil, heavy % 15.0 10.9 9.7 9.9 7.1
Coke, heavy % 1.8 2.1 2.0 2.4 2.3
Transformation efficiency, heavy % 85.0 89.0 90.3 90.1 92.8
Octane value (chromatography) 91.4 91.4 92.3 92.6 93.9
Gasoline selective, % 56.5 57.4 54.7 55.4 51.5
The lightweight oil selectivity, % 77.2 73.8 71.0 69.0 66.9
Coke selectivity, % 2.12 2.36 2.21 2.66 2.48
The dry gas selectivity, % 0.82 1.12 1.46 1.44 1.77
C
3+ C
4Selectivity, % 19.6 22.7 25.4 26.9 29.0
List following examples in order to be illustrated more clearly in the present invention, but its to scope of the present invention without any restriction.
Embodiment 1
30 gram (butt) NaY(SiO
2/ Al
2O
3=5.2) add 300 milliliters of about 10% ammonium sulfate solutions, stir, under 95-100 ℃, slowly add 150 milliliters of 10%(weight) oxalic acid and ammonium oxalate (both ratios are 2: 3) mixture aqueous solution, adding the back continues to stir 1 hour, filter, washing, 600 ℃ of wet cakes were handled 2 hours from steam.Repeat said process more once.Product through count heavy after in the ratio of every gram solid 10 ml solns, at 95 ℃, the ammonium fluoride aqueous solution with 2% is handled once, filters washing, 120 ℃ of oven dry, new-type high silicon Y zeolite (NHSY-C).Main analytical results is as follows:
a
00 Relative crystallinity % Na
2O % structural breakdown temperature ℃ specific surface m
2/ g
24.423 96 0.35 1062 854
Embodiment 2
30 gram (butt) NaY(SiO
2/ Al
2O
3=5.2) ammonium sulfate solution that adds 300 milliliters about 10% stirs, be warming up to 95-100 ℃ and slowly add 150 milliliters of 10%(weight) oxalic acid and ammonium oxalate mixture aqueous solution, adding the back continues to stir 1 hour, filter, washing, 600 ℃ of wet cakes were handled 2 hours from steam, product with 300 milliliters of about 10% ammonium sulfate solutions in 95 ℃ of exchanges 1 hour, filtration, washing, filter cake adds 300 milliliter of 5% ammonium acetate aqueous solution making beating, be warming up to 60-65 ℃, slowly add 42 milliliter of 5% ammonium silicofluoride aqueous solution, after adding, being warming up to 90 ℃ continues to stir 2 hours, filter, washing is according to the sodium content requirement to product, filter cake can exchange once according to a conventional method with 5-10% ammonium sulfate, also can not exchange, last 120 ℃ of oven dry of filter cake get new-type high silicon Y zeolite (NHSY-B).Main analytical results is as follows:
a
0 
Relative crystallinity % Na
2O % structural breakdown temperature ℃ specific surface m
2/ g
24.470 96 0.24 1065 794
650 gram (butt) NaY(SiO
2/ Al
2O
3=5,3) add 6.5 premium on currency, add 650 gram ammonium sulfate stirrings again and be warming up to 95-100 ℃, the oxalic acid and the ammonium oxalate mixture aqueous solution that slowly add 3.3 liter of 10% weight add the back and continue to stir 1 hour, filter, washing, filter cake 600 ℃ of roastings 2 hours in the presence of steam.Repeat said process more once.Product through count heavy after in the ratio of every gram solid 10 ml solns, handle once with 2.5% ammonium fluoride aqueous solution at 95 ℃, filter, washing, more according to a conventional method with the ammonium sulfate solution exchange once, last filter cake is 120 ℃ of oven dry, zeolite product (NHSY-C).Main analytical results is as follows:
a
0 
Relative crystallinity % Na
2O % structural breakdown temperature ℃ Z specific surface m
2/ g
24.415 110 0.08 1083 0.024 867
NHSY-C and matrix are mixed with fluidized catalytic cracking catalyst, and the content of NHSY-C is 25%(weight in the catalyzer).Preparation process is as follows:
After NHSY-C is levigate, with the water glass (SiO that provides
2Be equivalent to matrix weight 65%) mix making beating, the Tai-Ace S 150 (Al that provides is provided
2O
3Be equivalent to matrix weight 25%) become glue, add sodium metaaluminate again after aging, aging again, add Tai-Ace S 150 at last and make system PH=3-4, add ammoniacal liquor again and transfer PH=5-6, after gel is crossed the homogeneous mill, spraying drying, microballoon sieve after washing again, remove salinity.Catalyzer be numbered F-C, its analytical results is as follows:
Na
2O% Al
2O
3% SiO
2% specific surface m
2/ g pore volume ml/g
0.16 27.02 72.10 287 0.346
By above-mentioned identical method, NHSY-B is mixed with matrix, make fluidized catalytic cracking catalyst, be numbered F-B.
For relatively, prepare a fluidized catalytic cracking catalyst that contains FSEY and make the contrast catalyzer.Earlier prepare FSEY with the ammonium silicofluoride dealuminzation.
Get NH
+ 4Exchange degree is 80% NH
4Y(butt SiO
2/ Al
2O
3=5.3) 560 grams add 6.5 liters in water, add NH
4Ac650 gram, making beating is warming up to 60-65 ℃, with 5280 milliliter of 5% ammonium fluosilicate solution slowly be added to system (, NH
4Be warming up to 80 ℃ after hour adding, stirred 2 hours, be warming up to 90 ℃ again and stirred 2 hours, filter, hot water wash, filter cake is more according to a conventional method with ammoniumsulphate soln exchange four times, after last filter cake is fully washed, 120 ℃ of oven dry, product FSEY.Main analytical results is as follows:
a
0 Relative crystallinity % structural breakdown temperature ℃ Z specific surface m
2/ g Na
2O%
24.417 99 1080 0.026 878 0.11
FSEY is mixed with matrix in 25: 75 ratio, make fluidized catalytic cracking catalyst, its preparation formality is with embodiment 3, and catalyzer is numbered F-A.Main analytical results is as follows:
Na
2O% Al
2O
3% SiO
2% specific surface m
2/ g pore volume ml/g
0.44 26.90 71.25 403 0.393
The another kind of comparative catalyst who uses among the present invention is F-O, and it is the commodity fluidized catalytic cracking catalyst that slag oil crack is produced stop bracket gasoline that is used for of a kind of USY of containing.This catalyzer mesolite content is greater than 30%(weight).
Embodiment 5
Catalyzer of the present invention and comparative catalyst's evaluation is carried out on the small fixed flowing bed device.Before the evaluation, catalyzer is handled through deactivation earlier, and its condition is 800 ℃, 100% steam-treated 10 hours.The service temperature of evaluating apparatus, weight hourly space velocity (WHSV) and catalyzer are all listed in the evaluation result table the ratio (C/O) of stock oil.It is as follows to estimate raw materials used oil properties:
Viscosity, ν
1004.65(centistokes(cst)) molecular-weight average 331
Carbon residue 0.276(weighs %) initial boiling point (℃) 252
Proportion 0.8524 distillates 10%(℃) 306
Refractive index 1.4924 distillates 50%(℃) 400
Flash-point 149(℃) distillate 90%(℃) 501
Condensation point+36(℃) final boiling point (℃) 501
Distillate % 93 entirely
Cracked reaction product is expressed as the weight percentage (heavy %) of concrete product to raw material, comprises following hydrogen and hydro carbons:
H
2Hydrogen
C
1Methane
C
2Ethane and ethene
C
3Propane and propylene
C
4Butane, Trimethylmethane and butylene
43-220 ℃ of gasoline boiling point
220-330 ℃ of diesel oil boiling point
Heavy oil boiling point＞330 ℃
Coke concentrate on the catalyzer coke and (or) predecessor of charcoal
Definition: the weight of the weight/raw material of yield of gasoline (weight %)=gasoline
The weight of transformation efficiency (weight %)=(raw material weight-heavy oil weight)/raw material
Gasoline selective (%)=gasoline (heavy %)/transformation efficiency (heavy %)
Lightweight oil selectivity (%)=(gasoline (heavy %)+diesel oil (heavy %))/
Transformation efficiency (heavy %)
Coke selectivity (%)=coke (heavy %)/transformation efficiency (heavy %)
Dry gas selectivity (%)=H
2+ C
1+ C
2(heavy %)/transformation efficiency (heavy %)
C
3+ C
4Hydrocarbon-selective (%)=C
3+ C
4(heavy %)/transformation efficiency (heavy %)
The evaluation result of catalyzer F-C of the present invention and F-B and comparative catalyst F-A and F-O is listed in respectively in the table 4,5,6,7, draw the yield of gasoline and the transformation efficiency comparison diagram (Fig. 2) of each catalyzer under the same reaction conditions according to data in the table, drawn gasoline selective, lightweight oil selectivity, coke selectivity, dry gas selectivity and the C of each catalyzer
3+ C
4Hydrocarbon-selective respectively with the graph of a relation of transformation efficiency shown in Fig. 3,4,5,6,7.By data in the table as seen, catalyzer of the present invention and comparative catalyst's octane value level error is few, and the chromatography octane value is all more than 91.Fig. 2 shows that with respect to the comparative catalyst, the yield of gasoline of catalyzer of the present invention and transformation efficiency are all higher.Fig. 3 and Fig. 4 show that respectively catalyzer comparison of the present invention has higher gasoline selective than catalyzer, and the lightweight oil selectivity is also better.Fig. 5 shows that the coke selectivity of each catalyzer is all good, and is similar each other.Fig. 6,7 shows that gas-selectively and the comparative catalyst of catalyzer F-B of the present invention are similar, and F-C is more better.The above results shows that catalyzer of the present invention has improved activity and selectivity, has shown the superiority with the new-type high silicon Y zeolite (NHSY-C and NHSY-B) of method preparation of the present invention.
Brief Description Of Drawings:
The different NHSY-C of Fig. 1 aluminium " fragment " content
Aluminium " fragment " content a＞b＞c
Fig. 2 activity of such catalysts relatively
(1) ordinate yield of gasoline, heavy %
(2) ordinate transformation efficiency, heavy %
Reaction conditions: 480 ℃ of temperature of reaction, WHSV～16.0, C/O～3.0
The relation of Fig. 3 gasoline selective and transformation efficiency
The relation of Fig. 4 lightweight oil selectivity and transformation efficiency
The relation of Fig. 5 coke selectivity and transformation efficiency
The relation of Fig. 6 dry gas selectivity and transformation efficiency
Fig. 7 C
3+ C
4The relation of hydrocarbon-selective and transformation efficiency
Claims (8)
1, a kind of fluidized catalytic cracking catalyst of forming by high-silicon Y-Zeolite and matrix, it is characterized in that, the active ingredient high-silicon Y-Zeolite that contains in the described catalyzer combines and is used alternatingly through chemical dealuminization and two kinds of processes of hydrothermal treatment consists and handles y-type zeolite and make, new-type high silicon Y zeolite by name, described matrix in the controlling catalyst process by active ingredient mix making beating with water glass, Tai-Ace S 150, sodium metaaluminate, become glue, step such as wear out, wear out forms.
2, the described catalyst activity component-new-type high silicon Y zeolite of a kind of claim 1, it is characterized in that: 1. the aluminium room of described skeleton structure of zeolite is few; 2. the aluminium distribution uniform of zeolite surfaces externally and internally; 3. non-framework aluminum " fragment " amount that contains in the skeleton structure of zeolite hole can be controlled arbitrarily; 4. zeolite has flourishing secondary pore structure; 5. contain the sodium amount in the zeolite and represent less than 1.0% with sodium oxide, preferably less than 0.5%, SiO
2/ Al
2O
3Than being generally 6-40, best 8-20, relative crystallinity is greater than 80%, more preferably greater than 90%.
3, the preparation method of the catalyst activity component-new-type high silicon Y zeolite of claim 2 is characterized in that, with y-type zeolite with the processing that hockets that combines of the chemical dealuminization shown in formula I or (II) and two kinds of processes of hydrothermal treatment consists:
Two kinds of process alternate treatment number of times of formula II are decided by the active ingredient performance demands.
4, according to the method for claim 3, it is characterized in that described chemical dealuminization process is at 25-100 ℃, be preferably in 50-95 ℃, use 1-20%(weight), preferably the dealuminzation enveloping agent solution of 2-10% was handled y-type zeolite 1-6 hour, and preferably 2-4 hour, the hydrothermal treatment consists process was 400-700 ℃ in temperature, preferably 500-600 ℃ was carried out 1-3 hour, preferably 1.5-2 hour, atmosphere water concentration 20-100%(volume), also can be to contain 30-50%(weight) zeolite self water vapor of water.
According to the method for claim 4, it is characterized in that 5, described dealuminzation complexing agent can be selected for use: organic acid, for example: ethylenediamine tetraacetic acid (EDTA), oxalic acid, sulphosalicylic acid; Alcamines for example can be selected trolamine etc. for use; Organic and inorganic acid salt for example can be selected ammonium oxalate, Neutral ammonium fluoride, ammonium silicofluoride, ammonium borofluoride etc. for use; The mixture of the above-mentioned complexing agent of also optional usefulness, for example oxalic acid and ammonium oxalate mixture etc., each time chemical dealuminization process can be selected identical or different complexing agent for use.
According to claim 3,4 or 5 method, it is characterized in that 6, described y-type zeolite can be with the NaY zeolite of synthetic, its silica alumina ratio (SiO
2/ Al
2O
3) should be greater than 4, more preferably greater than 4.5, can be with about 10%(weight in treating processes) ammoniumsulphate soln carry out the appropriateness exchange, also can introduce mixed rare-earth elements, make
Content in zeolite is 0.5-8%(weight), best 1-5%.
7, preparation contains the method for fluidized catalytic cracking catalyst of new-type high silicon Y zeolite, it is characterized in that, will be levigate by the new-type high silicon Y zeolite that claim 3,4,5 or 6 method make, be the 10-50% of catalyst weight by its amount, preferably the amount of 15-30% is mixed making beating earlier with water glass, adds Tai-Ace S 150 and becomes glue, and is aging, add sodium metaaluminate, aging again, make system PH=3-4 with Tai-Ace S 150, transfer PH=5-6 that gel is crossed the homogeneous mill with ammoniacal liquor again after, spraying drying, the washing of sieving, drying for standby.
8, contain the application of fluidized catalytic cracking catalyst in producing stop bracket gasoline of new-type high silicon zeolite, it is characterized in that, the catalyzer that claim 7 is made is in fluidized catalytic cracker, and operational condition comprises that with stock oil distillate contacts with residual oil routinely.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103386 CN1020369C (en) | 1989-05-26 | 1989-05-26 | Cracking catalyst containing new-type high silicon y zeolite |
| CN 92103788 CN1031500C (en) | 1989-05-26 | 1992-05-25 | Preparation of high-silicon Y-zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103386 CN1020369C (en) | 1989-05-26 | 1989-05-26 | Cracking catalyst containing new-type high silicon y zeolite |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92103788 Division CN1031500C (en) | 1989-05-26 | 1992-05-25 | Preparation of high-silicon Y-zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042558A true CN1042558A (en) | 1990-05-30 |
| CN1020369C CN1020369C (en) | 1993-04-28 |
Family
ID=4855100
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89103386 Expired - Fee Related CN1020369C (en) | 1989-05-26 | 1989-05-26 | Cracking catalyst containing new-type high silicon y zeolite |
| CN 92103788 Expired - Fee Related CN1031500C (en) | 1989-05-26 | 1992-05-25 | Preparation of high-silicon Y-zeolite |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92103788 Expired - Fee Related CN1031500C (en) | 1989-05-26 | 1992-05-25 | Preparation of high-silicon Y-zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1020369C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047105C (en) * | 1992-11-17 | 1999-12-08 | 中国科学院大连化学物理研究所 | Metallic zeolite catalyst for reaction of converting synthetic gas into dimethyl ether |
| CN1082832C (en) * | 1991-08-16 | 2002-04-17 | 国际壳版研究有限公司 | Catalyst compositions comprising modified zeolite of Y-type |
| CN103930206A (en) * | 2011-10-24 | 2014-07-16 | 道达尔炼油法国 | Process for preparing a mesopores-containing catalyst, catalyst thus obtained and use thereof in a hydroconversion process. |
| CN105536854A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst containing Y molecular sieve |
| CN105536855A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst containing Y molecular sieve |
| CN105712373A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Modified Y type molecular sieve and preparation method thereof |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
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| CN1036644C (en) * | 1993-11-05 | 1997-12-10 | 中国石油化工总公司 | Preparation method of skeleton rich silicon Y molecular sieve |
| CN101259419B (en) * | 2008-04-09 | 2010-06-23 | 哈尔滨六环石油化工技术开发公司 | Method for preparing solid acid catalyst |
| CN105694957B (en) * | 2014-11-27 | 2017-12-05 | 中国海洋石油总公司 | A kind of mononuclear aromatics is hydrogenated with lightening method |
| CN110104657B (en) * | 2019-06-11 | 2021-04-02 | 太原大成环能化工技术有限公司 | Preparation method of Y-type molecular sieve with high silica-alumina ratio |
-
1989
- 1989-05-26 CN CN 89103386 patent/CN1020369C/en not_active Expired - Fee Related
-
1992
- 1992-05-25 CN CN 92103788 patent/CN1031500C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082832C (en) * | 1991-08-16 | 2002-04-17 | 国际壳版研究有限公司 | Catalyst compositions comprising modified zeolite of Y-type |
| CN1047105C (en) * | 1992-11-17 | 1999-12-08 | 中国科学院大连化学物理研究所 | Metallic zeolite catalyst for reaction of converting synthetic gas into dimethyl ether |
| CN103930206A (en) * | 2011-10-24 | 2014-07-16 | 道达尔炼油法国 | Process for preparing a mesopores-containing catalyst, catalyst thus obtained and use thereof in a hydroconversion process. |
| CN105536854A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst containing Y molecular sieve |
| CN105536855A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst containing Y molecular sieve |
| CN105536854B (en) * | 2014-11-03 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method for preparing the hydrocracking catalyst containing Y molecular sieve |
| CN105536855B (en) * | 2014-11-03 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of preparation method of the hydrocracking catalyst containing Y molecular sieve |
| CN105712373A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Modified Y type molecular sieve and preparation method thereof |
| CN105712373B (en) * | 2014-12-04 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y and preparation method thereof |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
| CN112439444A (en) * | 2020-12-03 | 2021-03-05 | 榆林学院 | Preparation method and application of supported hierarchical porous solid acid bifunctional catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1065253A (en) | 1992-10-14 |
| CN1020369C (en) | 1993-04-28 |
| CN1031500C (en) | 1996-04-10 |
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