CN1005385B - Y-type molecular sieve cracking catalyst containing rare earths oxidate - Google Patents
Y-type molecular sieve cracking catalyst containing rare earths oxidate Download PDFInfo
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- CN1005385B CN1005385B CN86107531.5A CN86107531A CN1005385B CN 1005385 B CN1005385 B CN 1005385B CN 86107531 A CN86107531 A CN 86107531A CN 1005385 B CN1005385 B CN 1005385B
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Abstract
The present invention relates to a hydrocarbon cracking catalyst containing rare earth Y type molecular sieves. Rare earth in molecular sieves is in a form of RE2O3 or RE(OH)3, and the positions of exchangeable cations are occupied by H+, NH4+ or Na+. The X-ray powder diffraction spectrogram of the molecular sieves is similar to that of conventional H+ or NH4+ Y type molecular sieves, but a dispersive characteristic peak for RE2O3 or RE(OH)3 exists at the position where a 2theta angle is 27 to 29 degrees. The cracking catalyst is not only capable of effectively reducing hydrogen transfer reaction and obviously weakening unit cell shrinking phenomena during a thermally or hydrothermally ageing process, but also has the advantages of simple preparing method and good sodium resistance and heavy metal pollution resistance. The cracking catalyst is suitable for the catalytic cracking or hydrogen cracking of heavy oil, particularly heavy oil with a high sodium content.
Description
The invention relates to a kind of molecular sieve catalyst that is used for cracking hydrocarbon and preparation method thereof.Exactly, be about high Y zeolite Catalysts and its preparation method heavy oil cracking, that contain rare earth oxide of a kind of heavy oil that is applicable to, particularly sodium content.
Along with the development of petroleum refining industry to the deep processing direction, cracking stock oil is more and more heavier, and cracking catalyst is faced with the problem that how to reduce coking yield and improve preventing from heavy metal, anti-sodium pollutant performance.
In all reactions that taken place in catalytic cracking process, double molecule hydrogen transfering reaction is the key that influences coking yield.Reduce coking yield, must reduce hydrogen transfer reactions.Widely use at present rare earth-Y(REY) though its active component of type molecular sieve cracking catalyst (REY) has higher activity because RE wherein
3+Be on the cation position, in heat or hydrothermal aging process, can significantly suppress the framework of molecular sieve dealumination reaction, the result causes acid site excessive concentration in the molecular sieve, quickened (the JSMagee et al. of the hydrogen transfer reactions in the catalytic process, Zeolite Chemistry and Catalysis, ACS Mono-geaph, 171, P615,1976; JSMagee et al., Preprints, ACS23,10571978).Has high skeleton SiO
2/ Al
2O
3Super steady-Y(USY) though the type molecular sieve can reduce hydrogen transfer reactions effectively, in heat or hydrothermal aging process the structure cell shrinkage phenomenon can take place, and causes activity of such catalysts descend significantly (Usup3,994,800).
From the antifouling property of cracking catalyst, though on the document (Usup4,480,047, Usup4,499,197, GB2,116,868) once reported in carrier, add RE(OH)
3With the preventing from heavy metal pollution performance of raising cracking catalyst, but how to make it can resist the pollution of sodium, be not reported so far.In general, even the processing of sodium process advanced desalination also is difficult to remove fully in the crude oil, particularly organic sodium wherein is difficult to remove especially.These sodium make the acid sites of catalyzer poison at least, make molecular sieve structure destruction on the catalyzer at most.Therefore, how from catalyst themselves, particularly solving anti-sodium from the molecular sieve itself as active component and pollute, also is the problem that present cracking catalyst faced.
Above-mentioned variety of issue at present cracking catalyst existence, the purpose of this invention is to provide a kind of excellent selectivity of high reactivity and USY type molecular sieve catalyst of the REY of having concurrently type molecular sieve catalyst, and have the molecular sieve cracking catalyst of anti-sodium pollutant performance.The present invention also provides the preparation method of this molecular sieve cracking catalyst and molecules of active components sieve thereof simultaneously.
Molecular sieve cracking catalyst provided by the present invention is to be active ingredient with 5～40% the HY type molecular sieve that contains rare earth oxide, be aided with 95～60% with gluey Al(OH)
3For the semi-synthetic carrier of binding agent constitutes.Rare earth in the said active ingredient HY type molecular sieve is all with RE
2O
3State exist, the exchangeable cation position is H
+Or Na
+Occupy.Contain RE
2O
3The similar conventional H Y zeolite of X light powder diffraction spectrogram of HY type molecular sieve, but the former is the RE that a disperse is arranged on 27～29 ℃ of positions in 20 jiaos
2O
3Characteristic peak, the intensity of this characteristic peak depends on the content of rare earth.
X light powder diffraction spectrogram shown in Figure 1 has shown the constitutional features place of molecular sieve provided by the present invention.Diffraction spectrogram among the figure (1) is RE
2O
3, (2) are the RE that contains provided by the invention
2O
3HY type molecular sieve; (3) be the conventional H Y zeolite.
Our test shows: use RE
2O
3Or RE(OH)
3The structure cell that is adjusted in molecular sieve in heat or the hydrothermal aging process shrinks, and can make activity of such catalysts reach the level of REY type molecular sieve catalyst on the basis that keeps the USY type molecular sieve property selected.Our test also shows: RE
2O
3Or RE(OH)
3Easy and sodium reacts the RE in the molecular sieve
2O
3Or RE(OH)
3Existence improved the performance that the anti-sodium of molecular sieve pollutes greatly.
The said RE that contains among the present invention
2O
3HY type molecular sieve can adopt one of following method preparation:
Method (1): with RECl
3Solution is dispersed in the NaY type molecular sieve basoid for the treatment of crystallization, and adds an amount of NaOH the total alkalinity of colloidal state system is remained unchanged, RE(OH to be generated)
3Be deposited in be uniformly dispersed in the colloid after, at 80～120 ℃, preferably left standstill crystallization 20～24 hours under 95～100 ℃, get final product through steps such as filtration, washing, ammonium exchange, roastings then.
Method (2): with RECl
3Solution is dispersed in the NaY type molecular sieve alkaline slurry after the crystallization, RE(OH to be generated)
3Be deposited in be uniformly dispersed in the molecular sieve pulp after, get final product through steps such as filtrations, washing, ammonium exchange, roasting.
Used RECl in the preparation process
3Solution can be the mixing RECl of any composition
3Solution, but preferably rich La(La content is not less than 30%) earth solution.The consumption of rare earth should make RE in the molecular sieve
2O
3With Al
2O
3Molecular ratio be 0.11～1.50, be preferably 0.25～0.55.
The ammonium exchange can be adopted (NH
4)
2SO
4Solution carries out, and give-and-take conditions are: (NH
4)
2SO
4With the weight ratio of molecular sieve (burn base) be 0.5～2.0, be preferably 0.8～1.2(NH
4)
2SO
4The concentration of solution is 1～30%, is preferably 5～15%, and the exchange temperature is 35～150 ℃, is preferably 50～90 ℃, and be 5～60 minutes swap time, is preferably 10～30 minutes, and the exchange number of times is 1～3 time.
Molecular sieve after the ammonium exchange can wash before roasting, also can be after roasting, wash with carrier during the preparation catalyzer.
Roasting condition is: 450～750 ℃, and best 500～600 ℃, 0.5～3 hour.
Molecular sieve after an ammonium exchange and roasting can carry out the ammonium exchange second time and roasting.
To contain RE
2O
3HY type molecular sieve in required ratio (for example: molecular sieve: carrier is 5～40: 95～60) be dispersed in gluey Al(OH)
3In the semi-synthetic carrier for binding agent, promptly can be made into and contain RE
2O
3HY type molecular sieve catalyst.
Adopt the RE that contains provided by the present invention
2O
3HY type molecular sieve be the catalyzer that active component is made, not only can reduce hydrogen transfer reactions effectively, and in heat or hydrothermal aging process, can weaken the structure cell shrinkage phenomenon significantly.Its cracking selectivity is near conventional USY type molecular sieve catalyst, and its activity and hydrothermal stability are near conventional REY type molecular sieve catalyst.In addition, this catalyzer has the performance of anti-sodium, vanadium, nickel contamination simultaneously, and prepares easy.This catalyzer is applicable to and comprises heavy oil that particularly the heavy oil that sodium content is high is in catalytic cracking, the hydrocracking of interior hydro carbons.
The RE that contains provided by the present invention
2O
3The preparation method of HY type molecular sieve be equally applicable to the introducing of A type or X type molecular sieve, mordenite, supersiliceous zeolite (for example ZSM-5) middle-weight rare earths, the rare earth in the gained corresponding product is equally with RE
2O
3State exist, the catalyzer that makes thus all has and contains RE
2O
3The similar advantage of HY type molecular sieve.For example make and contain RE with method provided by the invention
2O
3HZSM-5 molecular sieve (SiO
2/ Al
2O
3=60) catalyzer, through 800 ℃, 100% steam-treated after 4 hours the pulse micro-inverse specific activity HZSM-5 molecular sieve catalyst to n-tetradecane improve 140～165%.
Following example will be made further instruction to the present invention.
Prepare by foregoing molecular sieve preparation method (1) and (2) and to contain RE
2O
3HY type molecular sieve a, b, c(see Table 1).
The preparation of molecular sieve a:
(1) 210.7 gram concentrated sodium silicate solution (SiO wherein
228%, Na
2O8.8%) with 150 gram deionized water dilutions, obtain water glass solution (I);
(2) restrain rare sodium aluminate solution (Na wherein with the above-mentioned concentrated sodium silicate solution of 17.2 grams and 23.9
2O17.1%, Al
2O
32.3%) reaction was at room temperature worn out 27 hours after the reaction, obtained 41.1 gram directed agents (II);
(3) (II) added in (I), after being uniformly dispersed, under agitation slowly add the dense sodium aluminate solution of 34.4 grams (Na wherein
2O22.3%, Al
2O
319.6%), adds the back and continue to stir 15 minutes, obtain basoid (III);
(4) under agitation with 39 gram AlCl
3Solution (is converted into Al
2O
3Content be 8.8%) with 44 milliliters of RECl
3Solution (is converted into RE
2O
3Content be 261.6 grams per liters, wherein La
2O
3〉=30%) mixing solutions adds in (III), and adds an amount of NaOH, and the total alkalinity that makes the colloidal state system is with (III), RE in these slurries
2O
3/ Al
2O
3Molecular ratio be 0.33;
(5) treat the middle RE(OH that generates of step (4))
3Be deposited in be uniformly dispersed in the colloid after, under 97 ± 1 ℃, left standstill crystallization 20 hours, the dope filtration after the crystallization, wash to pH9-10;
(6) according to (NH
4)
2SO
4: molecular sieve (base burns): H
2O=1: 1: the amount ratio 20(weight ratio), under 90 ℃, carry out ammonium exchange 0.5 hour, filter then, filter cake promptly got in 550 ℃ of following roastings and contains RE in 2 hours
2O
3HY type molecular sieve a.
The preparation of molecular sieve b:
(its molecular composition is Na with directed agents method crystallization NaY molecular sieve that make, that contain 70% mother liquor with 100 grams
2OAl
2O
35SiO
2NH
2O) slurries under agitation join 90 milliliters of RECl
3Solution (is converted into RE
2O
3Content be 261.6 grams per liters, wherein La
2O
3〉=30%) in, RE in the gained mixed serum
2O
3/ Al
2O
3Molecular ratio be 0.33.RE(OH to be generated)
3Be deposited in be uniformly dispersed in the molecular sieve pulp after, after filtration, wash, carry out ammonium exchange and roasting according to the preparation process (6) of molecular sieve a again and promptly get and contain RE to pH9～10
2O
3HY type molecular sieve b,
The preparation of molecular sieve c:
Molecular sieve b is carried out the ammonium exchange second time and roasting promptly to be got and contains RE
2O
3HY type molecular sieve c.
With the analysis revealed of X-ray fluorescent method (Japanese 3014-X light fluorescence analyser of science, pipe is pressed 1930 volts, tungsten target, EDDA crystal): RE during products molecule sieves to molecular sieve a, b, c
2O
3With Al
2O
3Molecular ratio be 0.33.Because under the pH condition of preparation molecular sieve, the rare earth of adding can only be with RE(OH before roasting)
3Form have and RE in the products molecule sieve
2O
3/ Al
2O
3The analytical results of molecular ratio this molecular ratio when feeding intake is consistent, and this explanation is with RE(OH at the preparation process middle-weight rare earths)
3Form all be deposited in the molecular sieve RE(OH during roasting)
3Be converted into RE
2O
3
With the analysis revealed of conventional x-ray powder diffraction to molecular sieve a, b, c: the x-ray diffraction spectra of molecular sieve a, b, c all is similar to the conventional H Y zeolite, but is the RE that a disperse is arranged on 27～29 ° of positions in 2 θ angles
2O
3Characteristic peak.
Listed zeolite single crystal born of the same parents size data is according to 533 crystal plane in the table 1, measures with reference to the described method of ASTM-D3942-80.Mensuration is the cuk α radiation of carrying out on Japan D-max/ III of science A type X-ray diffractometer, Ni filtering.
Example 4～7
Press the preparation method of molecular sieve b in the example 1～3, with different RE
2O
3Al
2O
3(molecular ratio) feed ratio is prepared and is contained RE
2O
3HY type molecular sieve d, e, f, g(see Table 2).
With the analysis revealed of X-ray fluorometric method (condition is with example 1～3): RE in the products molecule sieve to molecular sieve d, e, f, g
2O
3With Al
2O
3Molecular ratio be respectively 0.11,0.22,0.33,0.55.Because under the pH condition of preparation molecular sieve, the rare earth of adding can only be with RE(OH before roasting)
3Form have and RE in the products molecule sieve
2O
3/ Al
2O
3The analytical results of molecular ratio this molecular ratio when feeding intake is consistent, and this explanation is with RE(OH at the preparation process middle-weight rare earths)
3Form all be deposited in the molecular sieve RE(OH during roasting)
3Be converted into RE
2O
3
With the analysis revealed of conventional x-ray powder diffraction to molecular sieve d, e, f, g: the x-ray diffraction spectra of molecular sieve d, e, f, g all is similar to the conventional H Y zeolite, but is the RE that a disperse is arranged on 27～29 ° of positions in 2 θ angles
2O
3Characteristic peak.
Example 8
By the preparation method of foregoing molecular sieve catalyst, preparation * contains RE
2O
3HY type molecular sieve catalyst.
Get example 1～3, preparation contains RE in 4～7
2O
3Each 15 gram of HY type molecular sieve a, b, c, d, e, f, g (base burns), in mortar, soak respectively and wear into homogeneous slurry, then slurries to be added to 327 gram solid contents separately be 26%, with acidifying sub-Al(OH)
3Gel is the semi-synthetic carrier (Al of binding agent
2O
3: carclazyte=25: 75), after stirring, promptly got in 16 hours through 110 ℃ of dryings and to contain RE
2O
3HY type molecular sieve catalyst, successively with their called after catalyst A, B, C, D, E, F, G.
In order to compare, respectively with USY type molecular sieve (Al wherein
2O
321%, Na
2O＜0.5%, its single cell size is 24.55
) and hand over the REY type molecular sieve that two roastings become (RE wherein through conventional two
2O
319%, SiO
2/ Al
2O
3=4.9, Na
2O＜1.5%, its single cell size is 24.71A) make conventional USY type and conventional REY type molecular sieve catalyst as stated above, and called after catalyst I and J.
Example 9
RE(OH)
3Or/and RE
2O
3Have and weaken the characteristic that the molecular sieve structure cell shrinks in the catalyzer.
After 4 hours, the structure cell shrinkage degree has evident difference: contain RE through 800 ℃, 100% steam-treated for catalyst A, B, C, I
2The HY type molecular sieve of O weakens significantly than the structure cell shrinkage phenomenon of conventional USY type molecular sieve, and data see Table 3.
Example 10
Contain RE
2O
3HY type molecular sieve catalyst can reduce hydrogen transfer reactions effectively, have C
= 3, C
= 4The characteristics that gasoline yield height and coking yield are low.
On small fixed, carry out the little evaluation of living of heavy oil respectively through 800 ℃, catalyst A, B, C, the J of 100% steam-treated after 4 hours.Assessing terms is as follows: reactant is 300～500 ℃ of triumph wax oils (performance perameter sees Table 4), and temperature of reaction is 482 ℃, and agent-oil ratio is 3.0, and weight space velocity is 8 o'clock
-1, catalyst-assembly is 27 grams (20～40 order).Evaluation result sees Table 5.
Example 11
Adopt the different methods preparation, the fresh molecular sieve single cell varies in size contains RE
2O
3The activity of HY type molecular sieve catalyst all approach conventional REY type molecular sieve catalyst, be better than conventional USY type molecular sieve catalyst.
On the little anti-and pulse micro-inverse of light oil, carry out activity assessment respectively through catalyst A after 4 hours of 800 ℃, 100% steam-treated, B, C, I, J.The assessing terms of the little work of light oil is as follows: reactant is 200～300 ℃ of fraction solar oils, and temperature of reaction is that 460 ℃, agent-oil ratio are 3.0, and weight space velocity is 16 hours
-1The catalyzer loading amount is 5 grams (20～40 order).The assessing terms of the little work of pulse is as follows: reactant is a n-tetradecane, and sample size is 0.3 microlitre, and temperature of reaction is 460 ℃, and catalyst-assembly is 0.1 gram (20～40 order).Evaluation result sees Table 6.
Example 12
RE in the catalyzer
2O
3Content 2.0% when above, contain RE
2O
3The activity of HY type molecular sieve catalyst reach the level of conventional REY type molecular sieve catalyst, be better than conventional USY type molecular sieve catalyst.
Carry out activity assessment respectively through 800 ℃, catalyzer D, E, F, G, I, the J of 100% steam-treated after 4 hours on pulse micro-inverse, assessing terms is with example 11, and evaluation result sees Table 7.
Example 13
Contain RE
2O
3The activity stability of HY type molecular sieve catalyst approach conventional REY type molecular sieve catalyst, be better than conventional USY type molecular sieve catalyst.
Catalyst A after 800,100% water vapor is handled 4,8,12,14.5 hours respectively, B, I, J carry out activity assessment respectively on pulse micro-inverse, assessing terms is with example 11, and evaluation result as shown in Figure 2.Fig. 2 is the comparison diagram of several different catalysts activity stabilities, and curve among the figure (1) and (3) are represented the active downtrending of conventional REY type molecular sieve catalyst J and conventional USY type molecular sieve catalyst I respectively; Curve (2) expression contains RE
2O
3HY type molecular sieve catalyst A, the active downtrending of B.
From Fig. 2 the different amplitudes of each catalyst activity reduction as can be seen, the RE that contains provided by the present invention
2O
3The activity stability of HY type molecular sieve catalyst approach conventional REY type molecular sieve catalyst.
Example 14
Contain RE
2O
3HY type molecular sieve catalyst have the characteristic that anti-sodium pollutes.
(amount to and contain Na sodium content is identical
2O0.06%) contain RE
2O
3HY type molecular sieve catalyst C and conventional USY type molecular sieve catalyst I use pickling process " to make it contain the sodium amount and (be converted into Na respectively
2O content) increase by 0.5%, 1.0%, 1.5% on the original basis, the forward and backward catalyst sample of dirty sodium is through 800 ℃, 100% steam-treated its activity of evaluation on pulse micro-inverse respectively after 4 hours, and assessing terms is with example 11, and evaluation result as shown in Figure 3.Fig. 3 is the comparison diagram of the anti-sodium pollutant performance of different catalysts, and curve among the figure (1) and (2) represent to contain RE respectively
2O
3HY type molecular sieve catalyst C and conventional USY type molecular sieve catalyst I go up sodium content and catalyst activity reservation percentage ratio.
The relation of (cracking activity * 100% before the cracking activity behind the catalyst contamination sodium/catalyst contamination sodium).
As can be seen from Figure 3: the RE that contains provided by the present invention
2O
3The anti-sodium pollutant performance of HY type molecular sieve catalyst be better than conventional USY type molecular sieve catalyst, the contamination level of sodium reaches 1.5%Na on catalyzer
2During O, the former activity still can keep 50%, and the latter only keeps 25%.
. it is as follows to soak the sodium method: with catalyst sample grinding powder (～150 order), through 500 ℃ of roastings after 2 hours with the NaCl aqueous solution thorough mixing of example weight 1/2, then 120 ℃ down oven dry promptly get the catalyst samples of sodium pollution.
Example 15
Contain RE
2O
3The anti-pollution of vanadium performance of HY type molecular sieve catalyst be better than conventional USY type molecular sieve catalyst.
To contain RE
2O
3HY type molecular sieve catalyst C and conventional USY type molecular sieve catalyst I respectively with the V of calculated amount
2O
5Powder fully mixes in mortar and grinds, and compression molding is got its 20～40 mesh sieve branch after the fragmentation then.Catalyst sample C, the I that the vanadiumcontent that so makes is respectively 5000ppm, 10000ppm and does not contain vanadium carries out the mensuration of pulse micro-inverse activity assessment and relative crystallization reservation degree respectively after 4 hours through 800 ℃, 100% steam-treated.The pulse micro-inverse assessing terms is with example 11, and evaluation result keeps percentage ratio (implication is with example 14) expression with activity.Relatively crystallization reservation degree is with the ratio value representation of the forward and backward X diffraction peak intensity in ° position, 2 θ=23.65 of catalyst sample hydrothermal treatment consists.The results are shown in Table 8.
Claims (20)
1, a kind of Y zeolite cracking catalyst that contains rare earth is characterized in that:
(a) it is an active ingredient with 5～40% the HY type molecular sieve that contains rare earth oxide, be aided with 95～60% with gluey AL(OH)
3For the semi-synthetic carrier of binding agent constitutes;
(b) rare earth in the molecular sieve is all with RE
2O
3State exists, and the exchangeable cation position is by H
+Or Na
+Occupy, the similar conventional H Y zeolite of the X light powder diffraction figure of this molecular sieve, but the RE of a disperse is arranged on 27～29 ° of positions
2O
3Characteristic peak [among Fig. 1 (2)];
(c) the HY type molecular sieve that contains rare earth oxide can make by following step:
(1) with the mixing RECl of any composition
3Solution is dispersed in the NaY molecular sieve basoid for the treatment of crystallization, and adds an amount of NaOH the total alkalinity of colloidal state system is remained unchanged, and the rare earth consumption should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.11～1.50;
(2) RE(OH to be generated)
3Be deposited in be uniformly dispersed in the colloid after, left standstill crystallization 20～24 hours, filtration washing under 80～120 ℃;
(3) with 1～30%(NH
4)
2SO
4Solution carries out ammonium exchange (NH
4)
2SO
4: molecular sieve (base burns)=0.5～2.0(weight ratio), 35～150 ℃ exchange 1～3 time, exchange 5～60 minutes at every turn;
(4) 450～750 ℃ of following roastings 0.5～3 hour;
Molecular sieve after an ammonium exchange and roasting can carry out the ammonium exchange second time and roasting;
(d) the HY type molecular sieve that contains rare earth oxide also can make by following step:
(1) with the mixing RECl of any composition
3Solution is dispersed in the NaY type molecular sieve alkaline slurry after the crystallization, and the rare earth consumption should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.11～1.50;
(2) RE(OH to be generated)
3Be deposited in be uniformly dispersed in the molecular sieve pulp after, filter washing;
(3) with 1～30%(NH
4)
2SO
4Solution carries out ammonium exchange, (NH
4)
2SO
4: molecular sieve (base burns)=0.5～2.0(weight ratio), 35～150 ℃ exchange 1～3 time, exchange 5～60 minutes at every turn;
(4) 450～750 ℃ of following roastings 0.5～3 hour;
Molecular sieve after an ammonium exchange and roasting can carry out the ammonium exchange second time and roasting.
2,, it is characterized in that (c) (1) and (d) said mixing RECl in (1) according to the described catalyzer of claim 1
3Solution is that La content is not less than 30% rich La earth solution, and the rare earth consumption should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.25～0.55.
3,, it is characterized in that said crystallization temperature is 95～100 ℃ in (C) (2) according to the described catalyzer of claim 1.
4, according to the described catalyzer of claim 1, it is characterized in that (c) (3), (d) said ammonium give-and-take conditions are in (3): with 5～15%(NH
4)
2SO
4Solution, (NH
4)
2SO
4Molecular sieve (base burns)=0.8～1.2(weight ratio), 50～90 ℃ of exchanges down exchange 10～30 minutes at every turn.
5, according to the described catalyzer of claim 1, it is characterized in that (c) (4), (d) said maturing temperature is 500～600 ℃ in (4).
6, the described molecular sieve catalyst of claim 1 is used for heavy oil, particularly the catalytic cracking of the heavy oil that sodium content is high, hydrocracking.
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|---|---|---|---|
| CN86107531.5A CN1005385B (en) | 1986-12-06 | 1986-12-06 | Y-type molecular sieve cracking catalyst containing rare earths oxidate |
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|---|---|---|---|
| CN86107531.5A CN1005385B (en) | 1986-12-06 | 1986-12-06 | Y-type molecular sieve cracking catalyst containing rare earths oxidate |
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| CN1005385B true CN1005385B (en) | 1989-10-11 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052666C (en) * | 1994-12-26 | 2000-05-24 | 北京燕山石油化工公司化工二厂 | Zeolite catalyst for synthesizing cumine and method for preparing cumin by using said catalyst |
| CN100496701C (en) * | 2004-03-04 | 2009-06-10 | 白相才 | High specific surface area rare earth silicon aluminium composite oxide and preparation method and adsorbent |
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| CN1322928C (en) * | 2004-08-13 | 2007-06-27 | 中国石油化工股份有限公司 | Cracking catalyst for reducing alkene content in catalytically cracked gasoline |
| CN100344374C (en) * | 2004-08-13 | 2007-10-24 | 中国石油化工股份有限公司 | Rare earth Y molecular screen and process for preparing the same |
| RU2548362C2 (en) | 2009-06-25 | 2015-04-20 | Чайна Петролеум & Кемикал Корпорейшн | Catalyst for catalytic cracking and method of increasing catalyst selectivity (versions) |
| CN102502695B (en) * | 2011-10-27 | 2014-08-27 | 湖南大学 | NaY molecular sieve modifying method |
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-
1986
- 1986-12-06 CN CN86107531.5A patent/CN1005385B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052666C (en) * | 1994-12-26 | 2000-05-24 | 北京燕山石油化工公司化工二厂 | Zeolite catalyst for synthesizing cumine and method for preparing cumin by using said catalyst |
| CN100496701C (en) * | 2004-03-04 | 2009-06-10 | 白相才 | High specific surface area rare earth silicon aluminium composite oxide and preparation method and adsorbent |
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|---|---|
| CN86107531A (en) | 1988-08-03 |
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