CN1020369C - Cracking catalyst containing new-type high silicon y zeolite - Google Patents
Cracking catalyst containing new-type high silicon y zeolite Download PDFInfo
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Abstract
The present invention discloses a fluid catalytic cracking catalyst containing a novel high silica zeolite. The novel high silica zeolite is prepared from Y type zeolite after the alternate treatment of the two processes of chemical aluminum removal and water thermal treatment. Compared with those of the prior art singly using one process, the treatment conditions are more moderate and simple, and the treatment has the advantages of short treating time, low cost and high flexibility. The product of the treatment has the advantages of high crystallization degree, low sodium content, good thermal stability of heat and water and strong selectivity; the catalyst prepared by the treatment is suitable for treating various petroleum hydrocarbons comprising heavy oil or residual oil; the performance of the catalyst is superior to that of the similar catalysts.
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 requiring institute to contain 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, and (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 is as formula I or J Tianjin) shown in, be to combine 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.
Claim the B method, 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, and 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
27AlMAS-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.Measure with the X-ray diffraction method of routine, make internal standard substance, measure 2 θ and equal near 54 ° and 58.3 ° diffraction angle with silica flour; 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), the halfwidth at the diffraction peak height that (555,751) (644) are located 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.(table 1-table 7 is seen the literary composition back)
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.
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:
Relative crystalline texture avalanche specific surface
a
0，
Na
2O%
Degree % temperature ℃ m
2/ g
24.423 96 0.35 1062 854
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:
Relative crystalline texture avalanche specific surface
a.
Na
2O%
Degree % temperature ℃ 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 ℃, slowly add the oxalic acid and the ammonium oxalate mixture aqueous solution of 3.3 liter of 10% weight, adding the back continues 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:
Structure collapses
Tie specific surface relatively
A.
Na
2The O% temperature Z that collapses
% ℃ of m of crystalline substance degree
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 pore volume
m
2/g 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.
Embodiment 4
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
4The Ac650 gram, making beating is warming up to 60-65 ℃.Slowly be added to 5280 milliliter of 5% ammonium fluosilicate solution in the system, be warming up to 80 ℃ after adding in about 4 hours, 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 was fully washed, 120 ℃ of oven dry got product FSEY.Main analytical results is as follows:
Structure collapses
Tie specific surface relatively
A.
The temperature of collapsing Z Na
2O%
% ℃ of m of crystalline substance degree
3/ g
24.471 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:
The specific surface pore volume
Na
2O% Al
2O
3% SiO
2% m
2/g 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).
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, and 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 (weight %) 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 zeolite＞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 %)/transform
Rate (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 selecting property of gasoline, 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/0～3.0
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
The stability of the high-silicon Y-Zeolite of table 1 distinct methods preparation relatively
Behind the front Steam treatment of Steam treatment
Sample preparation methods NaO2Heavy
Xi a. structural breakdown temperature Xi a.
% %
℃ %
Ammonium fluosilicate dealuminzation method 0.65 92 24.45 1,086 88 24.28
B method 0.24 97 24.48 1,071 92 24.28 of the present invention
C method 0.33 92 24.44 1,056 92 24.26 of the present invention
Hydrothermal dealumination method-93 24.45 1,002 80 24.19
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
Surface-area m
2/ g
Sample preparation methods a.
Micro pore volume ml/g
S
AlwaysS
InS
Greatly
Ammonium silicofluoride dealuminzation method 24.45 727 12 27 0.251
B method 24.47 794 53 78 0.244 of the present invention
C method 24.44 854 133 34 0.254 of the present invention
Hydrothermal dealumination method 24.52 759 83 7 0.253
* 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.
The Si/Al(I)
*The Si/Al(II)
Ammonium silicofluoride dealuminzation method 24.471 5.86 22.0
The inventive method 24.415 6.80 11.2
Hydrothermal dealumination goes 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 same selectivity of lightweight, % 75.4 72.04 70.7 67.1
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 26.32 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 7.9 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 16.69 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
Claims (5)
1, a kind of fluidized catalytic cracking catalyst is characterized in that, described catalyzer is made up of new-type high silicon Y zeolite and inorganic oxide matrix, and the shared therein ratio of new-type high silicon Y zeolite is 10-50%, and sodium oxide content is less than 1.0% (weight), SiO in the zeolite
2/ Al
2O
3Than being 6-40, relative crystallinity is greater than 80%; Inorganic oxide matrix can be selected from: aluminium oxide-silicon oxide, silica gel or silicon sol, aluminium glue or activated alumina, natural clay or their mixture; Described catalyzer is made by following method:
One, with SiO
2/ Al
2O
3Than the NaY zeolite greater than 4.5 synthetic is raw material, and the method that adopts chemical dealuminization and two kinds of processes of hydrothermal treatment consists to combine and hocket prepares new-type high silicon Y zeolite by following graphic and condition:
Following formula represents that chemical glue aluminium and two kinds of processes of hydrothermal treatment consists can hocket arbitrarily repeatedly, and which is preparation process terminate in and depend on requirement to product property in step;
(1) chemical dealuminization: temperature is 25-100 ℃, handles Y zeolite 1-6 hour with the dealumination agent solution (its consumption calculates by required pre-dealuminzation degree) of 1-20% (weight), and dealumination agent is selected from organic acid, comprises ethylenediamine tetraacetic acid (EDTA), oxalic acid, sulphosalicylic acid; Organic and inorganic salt comprise ammonium oxalate, Neutral ammonium fluoride, ammonium silicofluoride, ammonium borofluoride, and each time chemical dealuminization process can be selected identical or different dealumination agent for use, carries out ammonium ion exchange in the time of chemical dealuminization;
(2) hydrothermal treatment consists: treatment temp 400-700 ℃, treatment time 1-3 hour, atmosphere water concentration 20-100% (volume) also can be zeolite self water vapor that contains 30-50% (weight) water;
(3) chemical dealuminization: select the condition in (1) for use;
(4) hydrothermal treatment consists: select the condition in (2) for use;
(5) chemical dealuminization: proceed the zeolite framework dealuminzation, then select the condition in (1) for use; When only taking off non-framework aluminum, then use 1-5% (weight) NH
4F or (NH
4)
2C
2O
4Solution, consumption were handled zeolite 0.5-3 hour by every gram zeolite 5-10 ml soln under 50-100 ℃ of temperature;
Two, prepared new-type high silicon Y zeolite is levigate, mix dozen oar by its amount with water glass for the 10-50% elder generation of catalyst weight, add Tai-Ace S 150 and become glue, add sodium metaaluminate again after wearing out, 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, wash again after thus obtained microsphere sieves and remove salinity, be drying to obtain described catalyzer again.
According to the catalyzer of claim 1, it is characterized in that 2, the sodium oxide content of wherein contained new-type high silicon Y zeolite is less than 0.5%(weight), SiO
2/ Al
2O
3Than being 8-20, relative crystallinity is greater than 90%.
3, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that described method comprises:
One, with SiO
2/ Al
2O
3Than the NaY zeolite greater than 4.5 synthetic is raw material, and the method that adopts chemical dealuminization and two kinds of processes of hydrothermal treatment consists to combine and hocket prepares new-type high silicon Y zeolite by following graphic and condition:
Following formula represents that chemical dealuminization and two kinds of processes of hydrothermal treatment consists can hocket arbitrarily repeatedly, and which is preparation process terminate in and depend on requirement to product property in step;
(1) chemical dealuminization: temperature is 25-100 ℃, uses 1-20%(weight) dealumination agent solution (its consumption calculates by required pre-dealuminzation degree) handled Y zeolite 1-6 hour, dealumination agent is selected from organic acid, comprises ethylenediamine tetraacetic acid (EDTA), oxalic acid, sulphosalicylic acid; Organic and inorganic salt comprise ammonium oxalate, Neutral ammonium fluoride, ammonium silicofluoride, ammonium borofluoride, and each time chemical dealuminization process can be selected identical or different dealumination agent for use, carries out ammonium ion exchange in the time of chemical dealuminization;
(2) also can be to contain 30-50%(weight hydrothermal treatment consists: treatment temp 400-700 ℃, treatment time 1-3 hour, atmosphere water concentration 20-100%(volume)) zeolite self water vapor of water;
(3) chemical dealuminization: select the condition in (1) for use;
(4) hydrothermal treatment consists: select the condition in (2) for use;
(5) chemical dealuminization: proceed the zeolite framework dealuminzation, then select the condition in (1) for use; When only taking off non-framework aluminum, then use 1-5%(weight) NH
4F or (NH
4)
2C
2O
4Solution, consumption were handled zeolite 0.5-3 hour by every gram zeolite 5-10 ml soln under 50-100 ℃ of temperature;
Two, prepared new-type high silicon Y zeolite is levigate, mix making beating by its amount with water glass for the 10-50% elder generation of catalyst weight, add Tai-Ace S 150 and become glue, add sodium metaaluminate again after wearing out, 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, wash again after thus obtained microsphere sieves and remove salinity, dry again that catalyzer is standby.
4, according to the method for preparing catalyst of claim 3, it is characterized in that,
One, the method for preparing new-type high silicon Y zeolite only chemical dealuminization and two kinds of processes of hydrothermal treatment consists are hocketed twice, and process condition is:
(1) chemical dealuminization: temperature is 50-100 ℃, the dealumination agent oxalic acid and/or the ammonium oxalate aqueous solution, its concentration is 2-10%(weight), its consumption calculates by pre-dealuminzation degree, and the treatment time is 2-4 hour;
(2) hydrothermal treatment consists: temperature is 400-700 ℃, and the time is 1-2 hour, and the atmosphere water concentration is the 20-80%(volume);
(3) chemical dealuminization: select the condition in (1) for use;
(4) hydrothermal treatment consists: select the condition in (2) for use;
Two, the content of new-type high silicon Y zeolite in catalyzer is 15-30%(weight).
5, according to the method for preparing catalyst of claim 3, it is characterized in that:
One, the method for preparing new-type high silicon Y zeolite is only carried out twice chemical dealuminization and a hydrothermal treatment consists, and its process condition is followed successively by:
(1) chemical dealuminization: temperature is 50-100 ℃, the dealumination agent oxalic acid and/or the ammonium oxalate aqueous solution, its concentration is 2-10%(weight), its consumption calculates by pre-dealuminzation degree, and the treatment time is 2-4 hour;
(2) hydrothermal treatment consists: temperature is 400-700 ℃, and the time is 1-2 hour, and the atmosphere water concentration is the 20-80%(volume);
(3) chemical dealuminization: temperature is 60-90 ℃, and the dealumination agent ammonium silicofluoride aqueous solution, its consumption are every gram zeolite 5%(weight) ammonium fluosilicate solution 1-4 milliliter, treatment time 2-4 hour;
Two, the content of new-type high silicon Y zeolite in catalyzer is 15-30%(weight).
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 CN1042558A (en) | 1990-05-30 |
| CN1020369C true 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) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW223029B (en) * | 1991-08-16 | 1994-05-01 | Shell Internat Res Schappej B V | |
| 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 |
| 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 |
| WO2013060719A2 (en) * | 2011-10-24 | 2013-05-02 | Total Raffinage Marketing | Process for preparing a mesopores-containing catalyst, catalyst thus obtained and use thereof in a hydroconversion process. |
| 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 |
| 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 |
| 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 |
| 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 |
| CN112439444B (en) * | 2020-12-03 | 2023-07-04 | 榆林学院 | Preparation method and application of supported hierarchical pore solid acid bifunctional catalyst |
-
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
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042558A (en) | 1990-05-30 |
| CN1031500C (en) | 1996-04-10 |
| CN1065253A (en) | 1992-10-14 |
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