CN1179400A - Super-hydrophobic Y zeolite and its preparing process - Google Patents
Super-hydrophobic Y zeolite and its preparing process Download PDFInfo
- Publication number
- CN1179400A CN1179400A CN 96120049 CN96120049A CN1179400A CN 1179400 A CN1179400 A CN 1179400A CN 96120049 CN96120049 CN 96120049 CN 96120049 A CN96120049 A CN 96120049A CN 1179400 A CN1179400 A CN 1179400A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- hydrophobic
- super
- exchange
- water vapour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A superhydrophobic Y zeolite is prepared from the Y zeolite whose Na2O content is less than 0.2 Wt.% through treatment by steam at 550-700 deg. C and 0.01-1.0 MPa for 0.5-10hr and selectively chemical dealumination and SiO2/Al2O3 has such parameters as mole ratio: 5.0-25; crystal cell parameter: 24.25-24.40 A; specific surface area: 600-850 sq.m/g; Na2O content: less than 0.2 Wt.%; secondary pores greater than 20X10 to the power -10 m: 40% or more; the ratio of non-skeleton Al to total Al:15-80%; IR acidity: 0.20-0.60 mmol/g; etc. Said superhydrophobic Y zeolite can be used as acidic component of the catalyst to hydrocrack heavy VGO oil with excellent activity and selectivity.
Description
The present invention relates to a kind of super-hydrophobic Y zeolite that is used for cracking hydrocarbon and preparation method thereof.
The hydrocracking and the catalytic cracking of heavy oil fraction (＞350 ℃) are very important petroleum refining processes, mink cell focus can be converted into the high light-weight fuel oil of commercial value by this process.Although bigger progress is being arranged aspect catalyst activity and the selectivity improving for many years, particularly the work from acidic components-zeolite properties aspect of improving catalyzer has obtained bigger success.But further improve zeolite properties, the activity and the selectivity that improve cracking catalyst remain the direction that people make great efforts.
The UK2014970 patent has been described super-hydrophobic zeolite and preparation method thereof, with Na
2The NaNH of O content＜0.5w%
4Y molecular sieve is at 725 ℃-870 ℃, and the 0.02-1.0MPa water vapour pressure was handled 0.5-16 hour down, prepared super-hydrophobic Y zeolite.This zeolite has good hydrophobic performance, but its hydrothermal treatment consists temperature is very high, and greater than 725 ℃, the energy consumption height is at high like this Temperature Treatment Na
2O content is less than the Y zeolite of 0.5w%, and Y zeolite dealuminzation degree is very high, and the acidity of molecular sieve is very low.The acid site number of medium tenacity seldom, specific surface is low less than 550m
2/ g degree of crystallinity is also lower, and when being the hydrocracking catalyst hydrocracking heavy oil of acidic components with it, middle distillates oil selectivity is better, but active low.
It is a kind of zeolite with following character that the UK2014970 patent is described super-hydrophobic Y zeolite, at 25 ℃, and P/P
0Relative pressure is 0.10 hour, water adsorption amount＜5.00w%; Loading capacity＜0.070, propyl carbinol adsorption experiment residual value＜0.04w%.This patent has also been described the measuring method of these character of super-hydrophobic Y zeolite.
Loading capacity is measured: with 1: 100 ratio ion-exchange of weight ratio three times, each ion-exchange is all with the NaCl solution of newly preparing with anhydrous super-hydrophobic Y molecular sieve and 0.2M NaCl solution, and the filtration after drying records the Al of molecular sieve with weighting method
2O
3, Na
2O and SiO
2Content, loading capacity IEC=k[Na
2O/SiO
2], Na wherein
2O/SiO
2Be their mol ratio, k is the SiO of the molecular sieve before the ion-exchange
2/ Al
2O
3Mol ratio.
Propyl carbinol adsorption experiment residual value is measured: earlier with the 300 ℃ of roastings 16 hours in air of super-hydrophobic Y molecular sieve, in propyl carbinol: water: the ratio of molecular sieve=1: 100: 10 weight ratio is 25 ℃ of mixed stirrings 16 hours, get supernatant liquid, analyze the weight percent concentration of its propyl carbinol, promptly get propyl carbinol absorption residual value.
Water adsorption amount is measured: with the activation 16 hours under 425 ℃, 5mmHg pressure in air of super-hydrophobic Y molecular sieve, transfer to specified temperature and pressure then earlier, the planar water steam when reaching adsorption equilibrium, can record the water adsorption amount of super-hydrophobic Y molecular sieve.
The CN1041543A patent has been described a kind of preparation of super-hydrophobic Y zeolite, will be with (NH
4)
2SiF
6Y zeolite-the LZ-210 of dealuminzation places the high-temperature roasting stove, about 750 ℃ of hydrothermal treatment consists 16 hours, can prepare super-hydrophobic Y zeolite.
Temperature hydrothermal treatment consists LZ-210 zeolite at 750 ℃ high like this can cause the violent dealuminzation of LZ-210, and the super-hydrophobic Y zeolite acidity of preparation is very low.But this zeolite is when high-temperature water thermal treatment, and its degree of crystallinity keeps the degree height, and the micro pore volume of zeolite is many, secondary pore less (seeing document Zeolites, 1986,6.133).
The EP320247 patent has been described the acid treatment of super-hydrophobic Y zeolite.With certain density mineral acid leaching super-hydrophobic Y zeolite LZ-10, improve its surface-area and degree of crystallinity, but the super-hydrophobic Y zeolite that does not indicate after the acid treatment is to have ultra-hydrophobicity why.In fact, too much leach aluminium in the super-hydrophobic Y zeolite with mineral acid, at 25 ℃, P/Po is under 0.1 condition, and the water adsorption amount of the super-hydrophobic Y zeolite after the acid treatment is generally greater than 8w%, and LZ-10 is after acid treatment, its molecular sieve shows still be a kind of acid hydroxy group (seeing accompanying drawing 5), molecular sieve acidity after the acid treatment is still very low, and when being the hydrocracking catalyst hydrocracking heavy oil of acidic components with this kind molecular sieve, activity is lower.
The purpose of this invention is to provide a kind of have higher degree of crystallinity, specific surface, ratio, lattice constant and the secondary pore of suitable non-framework aluminum and total aluminium, the super-hydrophobic zeolite at the acid site of more medium tenacity and weak acid center and preparation method thereof.
We find, at lesser temps (550 ℃-700 ℃), roasting Na under the 0.01-1.0MPa water vapour pressure
2The Y zeolite of O content＜0.2w% can be prepared SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0, uses chemical process selectivity dealuminzation again, makes SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 6.5-25.Zeolite of the present invention has higher degree of crystallinity, specific surface than the super-hydrophobic Y zeolite of CN1041543 patent and UK2014970 patent preparation, ratio, the SiO of suitable non-framework aluminum and total aluminium
2/ Al
2O
3Mol ratio, lattice constant and secondary pore.Super-hydrophobic Y zeolite of the present invention has two or more surface acidity hydroxyl (seeing accompanying drawing 1,2 and 3), acid site and weak acid acid site with more medium tenacity.Super-hydrophobic Y zeolite with the present invention's preparation is the catalyst hydrogenation pressure fuel of acidic components, the catalyst activity height, and selectivity is good.
Of the present invention, have following feature: SiO
2/ Al
2O
3Mol ratio is 5.0-25, and unit cell parameters is 24.25-24.40 * 10
-10M,＞20 * 10
-10The secondary pore volume of m accounts for total more than 40%, specific surface 600-850m
2/ g, IR acidity 0.20-0.60mmol/g, Na
2O content＜0.2w%, non-framework aluminum account for the 15-80W% of the total aluminium of molecular sieve, at 25 ℃, and P/P
0Be 0.1 o'clock, water adsorption amount is less than 5w%, and propyl carbinol adsorption experiment residual value is less than 0.4, loading capacity＜0.07.The further feature of super-hydrophobic Y zeolite of the present invention is: SiO
2/ Al
2O
3Mol ratio is 6.0-17, unit cell parameters 24.25-24.35 * 10
-10M,＞20 * 10
-10M secondary micropore accounts for more than 50%, specific surface 700-800m
2/ g, IR acidity 0.25-0.50mmol/g, non-framework aluminum accounts for the 40-65w% of total aluminium.
Super-hydrophobic Y zeolite preparation method's of the present invention concrete steps are as follows:
1, Na
2O content is less than the preparation of the Y zeolite of 0.2w%
Na
2O content can prepare with following a or b method less than the Y zeolite of 0.2w%
A, be raw material with the NaY zeolite, with concentration is 1.0-5.0M, preferably the ammonium salt solution of 2.0-3.0M is exchange liquid, zeolite concentration in the exchange slurries is 0.05-1.0g/ml, preferably 0.1-0.5g/ml at 70-150 ℃, preferably stirred 1-2 hour for 80-120 ℃ time, repeat above-mentioned ion-exchange repeatedly, make Na
2The Y zeolite of O＜0.2w%.
B, be raw material with the NaY zeolite, with concentration is 1.0-5.0M, preferably the ammonium salt solution of 2.0-3.0M is exchange liquid, zeolite concentration in the exchange slurries is 0.05-1.0g/ml, 0.1-0.5g/ml preferably, under 70-150 ℃, preferably 80-120 ℃ was stirred 1-2 hour, ion-exchange 2-3 time makes Na
2O content is less than the Y zeolite product I of 3.0w%.
I places the high-temperature roasting stove with the Y zeolite product, at self water vapour or feed water vapour, 450 ℃-600 ℃, under the 0.01-0.2MPa water vapour pressure roasting 0.5-3.0 hour, makes product II.
Product II is carried out ion-exchange 3-4 time by the ion-exchange techniques and the ammonium salt solution that prepare product I, make Na
2O content is less than the Y zeolite of 0.2w%.
2, the Na that 1 step is prepared
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2w%, and at self water vapour or feeding water vapour, 550 ℃-700 ℃, the 0.01-1.0MPa water vapour pressure was handled 0.5-10 hour down, promptly got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y molecular sieve of 5.2-6.0.
3, the super-hydrophobic Y molecular sieve that 2 steps are obtained can get SiO with chemical process dealuminzation optionally
2/ Al
2O
3Mol ratio is the super-hydrophobic Y molecular sieve of 6.5-25.
4,3 method set by step, usable acid solution (hydrochloric acid, nitric acid, acetic acid, oxalic acid etc.) or organic complexing agent (as methyl ethyl diketone, ethylenediamine tetraacetic acid (EDTA) etc.) optionally remove the non-framework aluminum of zeolite.
Compared with prior art, super-hydrophobic Y zeolite preparation method of the present invention, the raw material Na of hydrothermal treatment consists
2O content is strict controlled in below the 0.2w%, is preferably in below the 0.15w%, under lower temperature 550-700 ℃, prepares super-hydrophobic Y zeolite under the 0.01-1.0MPa pressure, and preparation method's energy consumption of the present invention is low.
Compare with the super-hydrophobic Y zeolite of prior art for preparing, super-hydrophobic Y zeolite with preparation method's preparation of the present invention has higher degree of crystallinity, specific surface, the molecular sieve surface has two or more acid hydroxy groups, the acid site of more medium tenacity and weak acid center, ratio, lattice constant, silica alumina ratio and the secondary pore of suitable non-framework aluminum and total aluminium.During hydrocracking heavy oil, being that the catalyzer of acidic components is compared with super-hydrophobic Y zeolite with prior art for preparing, is that the catalyzer of acidic components has higher middle distillates oil selectivity and obvious high activity with the super-hydrophobic Y zeolite of the inventive method preparation.
Further describe the present invention below by example.
Fig. 1～Fig. 4 is respectively the surface hydroxyl infrared spectrogram of example 1～4 pairing super-hydrophobic Y zeolite, and Fig. 5～Fig. 8 is respectively the surface hydroxyl infrared spectrogram of reference example 5～8 pairing super-hydrophobic Y zeolites.
Example 1
(1) 1M
3Add 130kg industry NH in the liner enamelled swap tank
4NO
3(chemical plant, Dalian product, purity＞99.5%) adds 800 liters of industrial water purification, is made into 2M NH
4NO
3Solution is heated to 70 ℃, adds 120KgNaY zeolite (Wenzhou catalyst plant product, butt 50w%), stirs exchange 3 hours down at 70 ℃, repeats this exchange step 12 times, filters, and is washed to neutrality, obtains Na
2O content is 0.18% Y zeolite, oven dry.
(2) zeolite of above-mentioned washing oven dry is put into the high-pressure rotary stove, be rapidly heated to 650 ℃, at 1.0MPa, roasting is 6 hours under 100% water vapour pressure, obtains super-hydrophobic Y zeolite A of the present invention.Its physico-chemical property sees Table 1.Its surface hydroxyl infrared spectra is seen accompanying drawing 1.
Example 2
(1) gets 5.0kg NaY zeolite (with the example 1) NH that to be added to 50 liters of concentration be 2M
4NO
3In the solution, stir down at 100 ℃, ion-exchange 2 hours exchanges secondary altogether, and filter then, wash to neutrality, and oven dry, obtain product I.
(2) product I is placed the high-pressure rotary stove, at 550 ℃, roasting is 2 hours under the 100% water vapour 0.1MPa pressure, obtains product II.
(3) NH that product II is put into 50 liters of concentration is 2M
4NO
3In the solution, stir ion-exchange 2 hours down, exchange altogether 3 times, filter then, wash to neutrality at 100 ℃, and oven dry, product III obtained.
(4) with product III as in the high-pressure rotary stove, at 550 ℃, roasting is 4 hours under the 100% water vapour 0.2MPa pressure, obtains zeolite B of the present invention.Its physico-chemical property sees Table 1.Its surface hydroxyl infrared spectrum is seen accompanying drawing 2
Example 3
(1) in the NH4NO3 solution that 2.0kg NaY zeolite (with example 2) is added to 160 liters of concentration is 3M, stir ion-exchanges 0.5 hour down at 150 ℃, co-ion exchange 12 times obtains Na
2O content is 0.17% Y zeolite, and oven dry obtains product I.
(2) product I is put into the high-pressure rotary stove, at 700 ℃, 0.01MPa, roasting is 4 hours under 100% water vapour pressure, obtains product II.
(3) get product II 400g, putting into concentration is 4 liters of hydrochloric acid solns of 0.4M, handles 2 hours, filters, washs to neutral, and oven dry obtains super-hydrophobic Y zeolite C of the present invention.Its physico-chemical property sees Table 1, and the surface hydroxyl infrared spectra is seen accompanying drawing 3.
Example 4:
The super-hydrophobic Y zeolite A100 that example 1 is obtained restrains; Putting into concentration is 1 liter of methyl ethyl diketone solution of 0.4M, handles 2 hours, filters, and with 3 liters of deionized water wash, oven dry obtains super-hydrophobic Y zeolite D.Its physico-chemical property sees Table, and the surface hydroxyl infrared spectra is seen accompanying drawing 4.
Reference example 5
(1) NH that 3.0kg NaY zeolite (with example 1) is joined 18 liters of concentration is 2M
4NO
3In the solution, 90 ℃ of following ion-exchanges 1 hour, co-ion exchange 8 times, filtration, washing, drying obtain Na
2O content is 0.27% Y zeolite.
(2) Y zeolite behind the washing and drying is placed the high-pressure rotary stove, at 750 ℃, 0.1MPa, hydrothermal treatment consists is 6 hours under 100% water vapour pressure, obtains super-hydrophobic Y zeolite E.Its physico-chemical property sees Table, and the surface hydroxyl infrared spectra is seen accompanying drawing 5
Reference example 6
(1) NH that 1.0kg NaY zeolite (with example 1) is joined 8 liters of concentration is 1.5M
4NO
3In the solution, stir down at 100 ℃, ion-exchange 2 hours exchanges 2 times altogether, filters then, washs to neutrality, and oven dry obtains product I.
(2) with product I at 550 ℃, 0.1MPa under 100% water vapour pressure, high-pressure rotary kiln roasting 2 hours, obtains product II.
(3) with product II (1) ion-exchange 1 time set by step, obtain Na
2O content is the Y zeolite product III of 0.37W%.
(4) at 800 ℃, 0.1MPa, under 100% water vapour pressure, hydrothermal treatment consists product III 4h obtains super-hydrophobic Y zeolite F in the high-pressure rotary stove.Its physico-chemical property sees Table 1, and the surface hydroxyl infrared spectrum is seen accompanying drawing 6.
Reference example 7
The hydrochloric acid soln that it is 1.5M that the super-hydrophobic Y zeolite D600g that reference example 4 is obtained puts into 6 liters of concentration was handled 2 hours, filtered, washing is to neutral, and oven dry obtains Y zeolite G.Its physico-chemical property sees Table 1, and the surface hydroxyl infrared spectra is seen accompanying drawing 7.
Reference example 8: synthetic SiO
2/ Al
2O
3Than the LZ-210 zeolite (preparation method who is narrated with U.S. Patent number 4503023) that is 9: 1, press the method for United States Patent (USP) 4597956 narrations, the method with a kind of Tai-Ace S 150 crystallizing and washing processing washes out applied fluorochemical in this secondary synthesis step.With the LZ-210 zeolite that obtains in 100% water vapor 750 ℃ of hydrothermal treatment consists 16 hours, obtain super-hydrophobic Y zeolite H.Its physico-chemical property sees Table 1, and the surface hydroxyl infrared spectra is seen accompanying drawing 8.
The physico-chemical property of table 1 super-hydrophobic Y zeolite A-E
| Example | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 | ??8 |
| The zeolite numbering | ??A | ??B | ??C | ??D | ??E | ??F | ??G | ??H |
| Non-framework aluminum/total aluminium * 100% | ??75 | ??50 | ??45 | ??17 | ??86 | ??90 | ??15 | ???83 |
| Secondary pore (＞20 * 10 -10m)％ | ??50 | ??52 | ??56 | ??54 | ??53 | ??55 | ??58 | ???30 |
| IR acidity (mmol/g) | ??0.22 | ??0.33 | ??0.55 | ??0.30 | ??0.12 | ??0.15 | ??0.19 | ???0.17 |
| Na 2O?????w％ | ??0.15 | ??0.14 | ??0.10 | ??0.11 | ??0.26 | ??0.35 | ??0.23 | ???1.25 |
| Specific surface (BET method) m 2/g | ??630 | ??660 | ??780 | ??840 | ??520 | ??470 | ??750 | ???710 |
| SiO 2/Al 2O 3(mol ratio) | ??5.2 | ??6.0 | ??13.0 | ??23.9 | ??5.3 | ??5.4 | ??32.0 | ???9.4 |
| Unit cell parameters, 10 -10m | ??24.30 | ??24.32 | ??24.28 | ??24.30 | ??24.29 | ??24.28 | ??24.29 | ???24.30 |
| Loading capacity | ??0.051 | ??0.045 | ??0.057 | ??0.053 | ??0.041 | ??0.035 | ??0.060 | ???0.032 |
| Propyl carbinol absorption residual value | ??0.22 | ??0.25 | ??0.15 | ??0.17 | ??0.25 | ??0.22 | ??0.51 | ???0.43 |
| Water adsorption amount, 25 ℃ of P/P 0＝0.1w％ | ??4.3 | ??2.1 | ??4.0 | ??4.5 | ??3.0 | ??2.7 | ??10.2 | ???1.0 |
Reference example 9
Zeolite E with reference example 5 is acidic components, adds unformed carrier and hydrogenation metal component, makes hydrocracking catalyst E, and the evaluating catalyst result is as follows:
Table 2
| Catalyzer | R/E (R is a catalyst for refining) |
| Sample time (hour) | 800 |
| Stock oil (entering refining section) | Triumph VGO |
| Proportion d 20 4 | 0.9053 |
| EP℃ | 505 |
| Total N μ g/g | 2000 |
| Total S μ g/g | 3500 |
| BMCI | 43 |
Processing condition:
| Pressure MPa | 14.7 |
| Temperature R/D ℃ | 386/400 |
| During air speed R/D -1 | 1.0/1.5 |
| Gas/oil (volume ratio) | 1500 |
| The oily organonitrogen μ g/g of refining generation | 8 |
| Total run time (hour) | 1000 |
| Temperature raising speed | Substantially there is not temperature raising |
Generate oil:
| ＜370 ℃ of transformation efficiency w% | 70.3 |
| Middle distillates oil selectivity (boat coal+diesel oil/＜370 ℃ transformation efficiency) w% | 82.1 |
Example 10
With zeolite A of the present invention is acidic components, adds unformed carrier and hydrogenation metal component, oil type hydrocracking catalyst A in making.Evaluation result sees Table 3.
Table 3
| Catalyzer R/A |
| Sample time (hour) 800 |
| Stock oil (entering refining section) is with catalyzer D |
Processing condition:
| Pressure MPa | 14.7 |
| Temperature R/A ℃ | 386/380 |
| During air speed R/A -1 | 1.0/1.5 |
| Gas/oil (volume ratio) | 1500 |
| The oily organonitrogen μ g/g of refining generation | 7.5 |
| Total run time (hour) | 1100 |
| Temperature raising speed | Substantially there is not temperature raising |
Generate oil:
| ＜370 ℃ of transformation efficiency w% | 71.0 |
| Middle distillates oil selectivity (boat coal+diesel oil/＜370 ℃ transformation efficiency) w% | 84.2 |
Table 3 data show that A activity of such catalysts and selectivity all are significantly higher than the D catalyzer.Illustrate that super-hydrophobic Y zeolite hydrocracking heavy oil of the present invention has excellent middle oil selectivity and activity.
Example 11
Zeolite G with reference example 7 is acidic components, adds unformed carrier and hydrogenation metal, makes catalyzer F, and the evaluating catalyst result is as follows:
Table 4
| Catalyzer | R/F (R is a catalyst for refining) |
| Sample time (hour) | 700 |
| Stock oil (entering refining section) | Isolated island VGO mixes 10% wax tailings |
| Proportion d 20 4 | 0.9211 |
| EP℃ | 540 |
| Total N μ g/g | 2300 |
| Total S μ g/ | 3600 |
| BMCI | 47 |
Processing condition:
| Pressure MPa 12.0 |
| Temperature R/A ℃ 386/405 |
| During air speed R/A -1???????????????????????????1.0/1.5 |
| Gas/oil (volume ratio) 1400 |
| The oily organonitrogen μ g/g 15 of refining generation |
| Total run time (hour) 900 |
| Temperature raising speed does not have temperature raising substantially |
| Generate oil:＜370 ℃ of transformation efficiency w% 65.4 |
| Middle distillates oil selectivity (boat coal+diesel oil/＜370 ℃ transformation efficiency) w% 81.3 |
Example 12
With zeolite C of the present invention is acidic components, adds unformed carrier and hydrogenation metal, prepares catalyzer C.Evaluation result sees Table 5.
Table 5
| Stock oil: identical with the F catalyzer |
| Sample time (hour) 700 |
| Processing condition: pressure, air speed, hydrogen-oil ratio are all identical with the E catalyzer |
| Temperature R/C 382/378 |
| The oily organonitrogen 23 of refining generation |
| Total run time (hour) 1000 |
| Temperature raising speed does not have temperature raising substantially |
Generate oil:
| ＜370 ℃ of transformation efficiency w% 66.2 |
| Middle distillates oil selectivity 86.1 |
From table 5 data as can be seen, do the heavy oil feedstock of high difficult processing treatment, have excellent middle distillates oil selectivity and activity, be significantly higher than catalyzer E with the super-hydrophobic Y zeolite C of the present invention catalyzer C hydrocracking that is acidic components.
Claims (8)
1, a kind of super-hydrophobic Y zeolite is characterized in that SiO
2/ Al
2O
3Mol ratio is 5.0-25, and unit cell parameters is 24.25-24.40 * 10
-10M,＞20 * 10
-10The secondary pore of m accounts for more than 40%, specific surface 600-850m
2/ g, IR acidity 0.20-0.60mmol/g, Na
2O content＜0.2w%, non-framework aluminum account for the 15-80% of the total aluminium of molecular sieve, at 25 ℃, and P/P
0Be 0.1 o'clock, water adsorption amount is less than 5w%, and propyl carbinol adsorption experiment residual value is less than 0.4, loading capacity＜0.07.
2, by the zeolite of claim 1, it is characterized in that it being SiO
2/ Al
2O
3Mol ratio is 6.0-17, unit cell parameters 24.25-24.35 * 10
-10M,＞20 * 10
-10M secondary micropore accounts for more than 50%, specific surface 700-800m
2/ g, IR acidity 0.25-0.50mmol/g, non-framework aluminum accounts for the 40-65% of total aluminium.
3, a kind of preparation method of super-hydrophobic Y zeolite is characterized in that adopting following steps:
A, preparation Na
2The Y zeolite of O content＜0.2w%;
B, the zeolite that step a is obtained place the high-temperature roasting stove, at self water vapour or feed water vapour, 550 ℃-700 ℃, under the 0.01-1.0MPa water vapour pressure roasting 0.5-10 hour, make SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0;
C, super-hydrophobic Y zeolite that the b step is obtained obtain SiO with chemical process dealuminzation optionally
2/ Al
2O
3Mol ratio is 6.5～25 super-hydrophobic Y zeolite.
4, by the method for claim 3, it is characterized in that step a with solubility ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate etc., in the aqueous solution with the NaY zeolite at 70-150 ℃ of ion-exchange 0.5-3.0 hour, repeated exchanged is repeatedly prepared Na
2The Y zeolite of O content＜0.2w%.
5, by the method for claim 2, it is characterized in that to adopt following steps to produce Na
2The Y zeolite of O content＜0.2w%.
A, usefulness solubility ammonium salt and the ion-exchange of NaY zeolite, the exchange temperature is 70-150 ℃, 0.5-3.0 hour swap time, repeated exchanged twice obtains Na
2The Y zeolite product I of O content＜3.0w%;
B, the zeolite that step a is obtained place the high-temperature roasting stove, at self water vapour or feeding water vapour, 450 ℃-600 ℃, under the 0.01-0.20MPa water vapour pressure, roasting 0.5-3.0 hour, obtain product II;
C, product II is carried out ion-exchange 2-3 time again by a step, make Na
2The Y zeolite of O content＜0.2w%.
6, by the method for claim 2, the hydrothermal treatment consists temperature that it is characterized in that step b is 570 ℃-650 ℃, and water vapour pressure is 0.1-0.6MPa, and the hydrothermal treatment consists time is 2-6 hour.
7,, it is characterized in that step c optionally removes the non-framework aluminum of zeolite with acid solution (hydrochloric acid, nitric acid, acetic acid, oxalic acid etc.) or organic complexing agent (as methyl ethyl diketone, ethylenediamine tetraacetic acid (EDTA) etc.) by the method for claim 3.
8, by the method for claim 4 and 5, it is characterized in that adopting the concentration of exchange slurries mesolite in the ion-exchange step is 0.05-1.0g/ml, the soluble ammonium concentration of salt solution is 1M-4M, and the exchange temperature is 80 ℃-120 ℃, and be 1-2 hour swap time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120049A CN1053429C (en) | 1996-10-15 | 1996-10-15 | Super-hydrophobic Y zeolite and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120049A CN1053429C (en) | 1996-10-15 | 1996-10-15 | Super-hydrophobic Y zeolite and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1179400A true CN1179400A (en) | 1998-04-22 |
| CN1053429C CN1053429C (en) | 2000-06-14 |
Family
ID=5126097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120049A Expired - Lifetime CN1053429C (en) | 1996-10-15 | 1996-10-15 | Super-hydrophobic Y zeolite and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053429C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422081C (en) * | 2005-10-19 | 2008-10-01 | 中国石油化工股份有限公司 | Modified Y zeolite and its preparation method |
| CN102320621A (en) * | 2011-08-20 | 2012-01-18 | 广东科艺普实验室设备研制有限公司 | Hydrophobic modification method for Y-shaped molecular sieve |
| CN106672995A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| GB2546614B (en) * | 2014-12-01 | 2019-02-13 | China Petroleum & Chem Corp | H-Y Molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| CN114007736A (en) * | 2019-07-25 | 2022-02-01 | 东曹株式会社 | Hydrophobic zeolite, process for producing the same, and use thereof |
| CN115806299A (en) * | 2022-11-09 | 2023-03-17 | 复榆(张家港)新材料科技有限公司 | Multistage Kong Gaogui hydrophobic zeolite with FAU structure |
| CN115818661A (en) * | 2022-11-09 | 2023-03-21 | 复榆(张家港)新材料科技有限公司 | Preparation method of multistage Kong Gaogui hydrophobic zeolite with FAU structure |
| CN116282066A (en) * | 2022-12-22 | 2023-06-23 | 复榆(张家港)新材料科技有限公司 | Method for preparing hierarchical-pore high-silicon FAU zeolite from regenerated acidic mother solution |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1131195A (en) * | 1978-02-23 | 1982-09-07 | David E. Earls | Ultrahydrophobic zeolite y |
| US4331694A (en) * | 1978-12-26 | 1982-05-25 | Union Carbide Corporation | Removal of caffeine by selective adsorption using zeolite adsorbents |
| EP0020799A1 (en) * | 1979-06-15 | 1981-01-07 | Union Carbide Corporation | Treatment of exhaust gas streams |
| US4401556A (en) * | 1979-11-13 | 1983-08-30 | Union Carbide Corporation | Midbarrel hydrocracking |
| CN1041543A (en) * | 1988-09-01 | 1990-04-25 | 联合碳化公司 | The preparation of ultrahydrophobic zeolite |
-
1996
- 1996-10-15 CN CN96120049A patent/CN1053429C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422081C (en) * | 2005-10-19 | 2008-10-01 | 中国石油化工股份有限公司 | Modified Y zeolite and its preparation method |
| CN102320621A (en) * | 2011-08-20 | 2012-01-18 | 广东科艺普实验室设备研制有限公司 | Hydrophobic modification method for Y-shaped molecular sieve |
| GB2546614B (en) * | 2014-12-01 | 2019-02-13 | China Petroleum & Chem Corp | H-Y Molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| US10525452B2 (en) | 2014-12-01 | 2020-01-07 | China Petroleum & Chemical Corporation | Na-Y molecular sieve, H-Y molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method |
| CN106672995A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN106672995B (en) * | 2015-11-09 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y and preparation method thereof |
| CN114007736A (en) * | 2019-07-25 | 2022-02-01 | 东曹株式会社 | Hydrophobic zeolite, process for producing the same, and use thereof |
| CN115806299A (en) * | 2022-11-09 | 2023-03-17 | 复榆(张家港)新材料科技有限公司 | Multistage Kong Gaogui hydrophobic zeolite with FAU structure |
| CN115818661A (en) * | 2022-11-09 | 2023-03-21 | 复榆(张家港)新材料科技有限公司 | Preparation method of multistage Kong Gaogui hydrophobic zeolite with FAU structure |
| CN116282066A (en) * | 2022-12-22 | 2023-06-23 | 复榆(张家港)新材料科技有限公司 | Method for preparing hierarchical-pore high-silicon FAU zeolite from regenerated acidic mother solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053429C (en) | 2000-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1096296C (en) | Hydrocracking catalyst for producing middle distillate and its preparation method | |
| CN1107710C (en) | Hydrocracing catalyst containing modified beta zeolite and its preparing process | |
| CN1053429C (en) | Super-hydrophobic Y zeolite and its preparing process | |
| CN102773117A (en) | Medium-oil-type hydrocracking catalyst and preparation method thereof | |
| CN1064929C (en) | High silicon high crystallinity Y type molecular sieve and its preparing method | |
| CN1059701A (en) | High-silicon beta zeolite | |
| CN1058382A (en) | The preparation method of high-Si zeolite containing rare-earth five-membered ring structure | |
| CN1325378C (en) | Modified molecular sieve and its prepn process | |
| CN102974376B (en) | Catalytic cracking auxiliary agent and preparation method thereof | |
| CN1169717C (en) | Y-zeolite modifying method with RE ion and its product | |
| CN1094075C (en) | Gamma-zeolite contained middle distillate type hydrocracking catalyst and its preparation | |
| CN1415704A (en) | Cracking catalyst with hydrogen being added for noble metal and its prepn. method | |
| CN1031030A (en) | The preparation of low content of rare earth super-stable Y molecular sieves | |
| CN1221473C (en) | Combined zeolite comprising two kinds of modified Y-type zeolite | |
| CN111268689A (en) | Method for preparing mesoporous molecular sieve by ammonia-free method | |
| CN102974337B (en) | Catalytic cracking auxiliary agent and preparation method thereof | |
| CN102974331B (en) | Catalytic cracking auxiliary agent and preparation method thereof | |
| CN1307098C (en) | Method for preparing rare-earth ultrastable Y-type zeolite | |
| CN107345153A (en) | A kind of method for hydrogen cracking for producing low-coagulation diesel oil | |
| CN1147574C (en) | Hydrocracking catalyst for inceasing output of jet fuel and diesel oil | |
| CN106140281A (en) | A kind of preparation method of middle oil type hydrocracking catalyst | |
| CN1062750A (en) | The cracking catalyst of phosphorous and hyperastable Y-type RE zeolite | |
| CN1194072C (en) | RE-containing Si-base partially-synthesized hydrocarbon converting catalyst | |
| CN102974335B (en) | Catalytic cracking auxiliary agent and preparation method thereof | |
| CN106140280A (en) | A kind of hydrocracking catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20000614 |
|
| EXPY | Termination of patent right or utility model |