CN86107598A - Contain the molecular sieve and the preparation thereof of rare earth oxide - Google Patents
Contain the molecular sieve and the preparation thereof of rare earth oxide Download PDFInfo
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- CN86107598A CN86107598A CN86107598.6A CN86107598A CN86107598A CN 86107598 A CN86107598 A CN 86107598A CN 86107598 A CN86107598 A CN 86107598A CN 86107598 A CN86107598 A CN 86107598A
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Abstract
A kind of hydrocarbon cracking catalyzer that contains rare earth superstable Y-type molecular sieve, the rare earth of its molecular sieve are all with RE (OH)
3Or RE
2O
3State exists, and the exchangeable cation position is Na
+Or H
+Occupy; The similar conventional super-stable Y molecular sieves of the X light powder diffraction spectrogram of this molecular sieve, but in 2 θ angles be have on 27～29 ° of positions a disperse, RE (OH)
3Or RE
2O
3Characteristic peak.This cracking catalyst not only can reduce hydrogen transfer reactions effectively, in heat or hydrothermal aging process, weaken the structure cell shrinkage phenomenon significantly, and the preparation method is simple, product performance are stable, performance with anti-sodium and heavy metal contamination, be applicable to catalytic cracking or the high heavy oil of hydrocracking heavy oil, particularly sodium content.
Description
The invention relates to a kind of super steady-Y zeolite product that is used for cracking hydrocarbon and preparation method thereof.Exactly, be super steady-Y zeolite product and preparation method thereof about the high heavy oil cracking 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 J.S.Magee et al. of the hydrogen transfer reactions in the catalytic process, Zeolite Chemistry and Catalysis, ACS Monograph, 171, P615,1976; J.S.Magee et al., Preprints, ACS23,1057,1978).Has high skeleton SiO
2/ Al
2O
3Super steady-Y(USY) though the type molecular sieve can reduce hydrogen transfer reactions effectively, the structure cell shrinkage phenomenon can take place in heat or hydrothermal aging process cause activity of such catalysts descend significantly (USP3,994,800).
Improving the active relatively effective means of USY type molecular sieve is to introduce RE
3+, the concrete grammar of employing roughly is divided into two classes: the one, NaY type molecular sieve is exchanged a small amount of RE earlier
3+, carry out ammonium exchange or acid treatment after the roasting and make REUSY type molecular sieve (USP3,595,611; USP4,218,307); Be that NaY type molecular sieve is made USY type molecular sieve earlier again, and then exchange RE
3+Make REUSY type molecular sieve (Scherzer, J., Bass.J.L., J.Catal., 46,100,1977; Scherzer, J., Ronald E.Ritter, Ind.Eng.Chem.Prod.Res.Dev., 17 (3), 219,1978).Increase than USY type molecular sieve though this class REUSY type molecular sieve is active, molecular sieve performance is very responsive to preparation condition.
From the antifouling property of cracking catalyst, though (USP4,480,047 on the document; USP4,499,197; GB2,116,868) once reported and 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, also be difficult to remove fully even the sodium in the crude oil is handled through advanced desalination, 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 excellent selectivity that the purpose of this invention is to provide a kind of high reactivity and USY type molecular sieve of the REY of having concurrently type molecular sieve, and have the molecular sieve of anti-sodium pollutant performance, and with this active constituent as cracking catalyst.The preparation method that the present invention also provides this molecular sieve simultaneously and contained the cracking catalyst of this molecular sieve.
Molecular sieve provided by the present invention system contains the USY type molecular sieve of rare earth, and rare earth wherein is all with RE(OH)
3Or RE
2O
3State exists, and the exchangeable cation position is Na
+Or H
+Occupy.Contain RE(OH)
3Or RE
2O
3The X light powder diffraction spectrogram of USY type molecular sieve be similar to conventional USY type molecular sieve, but the former in 2 θ angles be have on 27～29 ° of positions a disperse, RE(OH)
3Or RE
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(OH)
3Or RE
2O
3; (2) be the RE(OH that contains provided by the invention)
3Or RE
2O
3USY type molecular sieve; (3) be conventional USY type molecular sieve.
Our test shows: use RE(OH)
3Or RE
2O
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(OH)
3Or RE
2O
3Easy and sodium reacts RE(OH in the molecular sieve)
3Or RE
2O
3Existence improved the performance that the anti-sodium of molecular sieve pollutes greatly.
The RE(OH that contains provided by the present invention)
2Or RE
2O
3USY type molecular sieve can adopt one of following method to be prepared into:
Method (1): with NH
4OH or other alkali (as NaOH, KOH etc.) and RECl
3Solution is with 3.0～4.0: the amount ratio 1(molecular ratio) reacts prepared gluey RE(OH)
3After filtration, after the washing, be evenly dispersed in the USY type molecular sieve pulp that is prepared into any method, get final product to such an extent that contain RE(OH)
3USY type molecular sieve.
Method (2): the RE that will make with any method
2O
3After grinding fully, be evenly dispersed in the USY type molecular sieve pulp that is prepared into any method, get final product to such an extent that contain RE
2O
3USY type molecular sieve.
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; Used RE
2O
3Can be the mixing RE of any composition
2O
3, but preferably rich La(La content is not less than 30%) RE
2O
3; The consumption of rare earth should make RE in the molecular sieve
2O
3With Al
2O
3Molecular ratio be 0.11～0.50, be preferably 0.25～0.55.
To contain RE(OH)
3Or RE
2O
3USY 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 contain RE(OH)
3Or RE
2O
3USY type molecular sieve catalyst.
Adopt the RE(OH that contains provided by the present invention)
3Or RE
2O
3USY 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 the preparation method is simple, product performance stable.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(OH that contains provided by the present invention)
3Or RE
2O
3The preparation method of USY 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(OH)
3Or RE
2O
3State exist, the catalyzer that makes thus all has and contains RE(OH)
3Or RE
2O
3The similar advantage of USY type molecular sieve catalyst.For example contain RE(OH) with what method provided by the invention made
3HZSM-5 molecular sieve (its SiO
2/ Al
2O
3=60) catalyzer is through the pulse micro-inverse specific activity HZSM-5 molecular sieve catalyst raising 140～165% to n-tetradecane after 4 hours of 800 ℃ of hydrothermal treatment consists.
Following example will be made further instruction to the present invention.
Example 1～5
By foregoing molecular sieve preparation method (1) and (2), adopt the single cell size
*Different USY type molecular sieves is with different RE
2O
3/ Al
2O
3(molecular ratio) feed ratio is prepared and is contained RE(OH)
3Or RE
2O
3USY type molecular sieve a, b, c, d, e(see Table 1).
Table 1
The preparation of molecular sieve a:
(1) under agitation with 7.2 milliliters of NH
4OH(NH
325～28%) be added to 30 milliliters of RECl
3Solution (is converted into RE
2O
3Content be 261.6 grams per liters, wherein La
2O
3〉=30%) in, the gained precipitation promptly gets RE(OH after filtration)
3;
(2) with RE(OH)
3Promptly got RE in 1 hour 350 ℃ of following roastings
2O
3, be ground into powder (～150 order);
(3) getting 100 gram single cells is 24.55
USY type molecular sieve (base, wherein Al burn
2O
321%, Na
2O＜0.5%) wet-milling becomes homogeneous slurry in mortar;
(4) with RE
2O
3Powder joins in the USY type molecular sieve pulp, treats promptly to get RE after it is uniformly dispersed
2O
3/ Al
2O
3Molecular ratio is 0.11 the RE that contains
2O
3USY type molecular sieve a.
The preparation of molecular sieve b:
(1) in the preparation with molecular sieve a (3);
(2) get commercial industrial product RE
2O
317.44 gram (content 90.0%) joins in the USY type molecular sieve pulp after grinding (～150 order), treats promptly to get RE after it is uniformly dispersed
2O
3/ Al
2O
3Molecular ratio is 0.22 the RE that contains
2O
3USY type molecular sieve b.
The preparation of molecular sieve C:
(1) 90 milliliter of RECl
3Solution (is converted into RE
2O
3Content be 261.6 grams per liters, wherein La
2O
3〉=30%) with 60 milliliters of deionized water dilutions, obtains RECl
3Solution (I);
(2) under agitation with 21.6 milliliters of NH
4OH(NH
325～28%) add in (I), the throw out that obtains after filtration, deionized water is washed till PH7～8 and promptly gets RE(OH)
3(II);
(3) getting 100 gram single cells is 24.55
USY type molecular sieve (base, wherein Al burn
2O
321%, Na
2O＜0.5%) wet-milling becomes homogeneous slurry (III) in mortar;
(4) (III) added in (II), promptly get RE after being uniformly dispersed
2O
3/ Al
2O
3Molecular ratio is 0.33 mixed serum (IV);
(5) (IV) after filtration, wash to PH8～9, promptly get contain RE(OH)
3USY type molecular sieve c.
The preparation method of molecular sieve d is identical with c, still:
(1) in 150 milliliters of RECl
3Solution dilutes with 100 milliliters of deionized waters;
(2) middle with 36 milliliters of NH
4OH;
That obtain (4) is RE
2O
3/ Al
2O
3Molecular ratio is 0.55 mixed serum.
The preparation method of molecular sieve e is identical with c, still:
(1) in 90 milliliters of RECl
3Solution dilutes with 60 milliliters of deionized waters;
(2) middle with 21.6 milliliters of NH
4OH;
(3) single cell of USY type molecular sieve is 24.35 in
;
That obtain (4) is RE
2O
3/ Al
2O
3Molecular ratio is 0.33 mixed serum.
With the analysis revealed of X-ray fluorometric method (Japanese 3014-X light florescence analysis instrument of science, pipe is pressed 1930 volts, tungsten target, EDDA crystal): RE during products molecule sieves to molecular sieve a, b, c, d, e
2O
3With Al
2O
3Molecular ratio be respectively 0.11,0.22,0.33,0.55,0.33.Because under the PH condition of preparation molecular sieve, the rare earth of adding can only be with RE(OH)
3Or RE
2O
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)
3Or RE
2O
3Form all is deposited in the molecular sieve.
With the analysis revealed of conventional x-ray powder diffraction to above-mentioned five sieve samples: their X light powder diffraction spectrogram all is similar to conventional USY type molecular sieve, but in 2 θ angles be have on 27～29 ° of positions a disperse, RE(OH)
3Or RE
2O
3Characteristic peak.
*Zeolite single crystal born of the same parents size is according to 533 crystal plane, measures with reference to the described method of ASTM-D3942-80.Mensuration is carried out CuK α radiation, Ni filtering on Japan D-max/ III of science A type X-ray diffractometer.
Example 6
By the preparation method of foregoing molecular sieve catalyst, prepare contain RE(OH)
3Or RE
2O
3USY type molecular sieve catalyst.
Get the RE(OH that contains that is prepared in the example 1～5)
3Or RE
2O
3Each 15 gram of USY type molecular sieve a, b, c, d, e (base burns), wet-milling becomes homogeneous slurry in mortar respectively, then slurries to be added to 327 gram solid contents separately be 26%, with acidifying SB-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 contain RE(OH)
3Or RE
2O
3USY type molecular sieve catalyst, called after catalyst A, B, C, D, E successively.
In order to compare, be 24.55 with the single cell size respectively
USY type molecular sieve (Al wherein
2O
321%, Na
2O＜0.5%) and through the two single cell sizes of handing over two roastings to become is 24.71
REY type molecular sieve (RE wherein
2O
319%, SiO
2/ Al
2O
3=4.9, Na
2O＜1.5%) make conventional USY type and conventional REY type molecular sieve catalyst as stated above respectively, and called after catalyst I and J.
Example 7
RE(OH)
3Or 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(OH through 800 ℃, 100% steam-treated for catalyzer C that USY zeolite single crystal born of the same parents size is identical and I)
3Molecular sieve than not containing RE(OH)
3The structure cell shrinkage phenomenon of molecular sieve weaken significantly, data see Table 2.RE
2O
3Also has same effect.
Table 2
Example 8
Contain RE(OH)
3Or RE
2O
3USY type molecular sieve catalyst can reduce hydrogen transfer reactions effectively, have C
3=, C
4=, gasoline yield height and the low characteristics of coking yield.
On small fixed, carry out the little evaluation of living of heavy oil respectively through 800 ℃, catalyzer C, I, 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 3), and temperature of reaction is 482 ℃, and agent-oil ratio is 3.0, and weight space velocity is 8 o'clock
-1, the catalyzer loading amount is 27 grams (20～40 order).Evaluation result sees Table 4.Catalyst B has similar result.
Example 9
The USY molecular sieve that adopts single cell to vary in size is prepared contains RE(OH)
3Or RE
2O
3The activity of USY type molecular sieve catalyst all approach conventional REY type molecular sieve catalyst, be better than conventional USY type molecular sieve catalyst.
On pulse micro-inverse, carry out activity assessment respectively through 800 ℃, catalyzer C, E, I, the J of 100% steam-treated after 4 hours.Assessing terms is as follows: reactant is a n-tetradecane, and sample size is 0.3 microlitre, and temperature of reaction is 460 ℃, and the catalyzer loading amount is 0.1 gram (20～40 order).Evaluation result sees Table 5.
Example 10
RE in the catalyzer
2O
3Content reach 2.0% when above, contain RE(OH)
3Or RE
2O
3The activity of USY type molecular sieve catalyst reached the level of conventional REY type molecular sieve catalyst, be better than conventional USY type molecular sieve catalyst.
On pulse micro-inverse, carry out activity assessment respectively through 800 ℃, catalyst A, B, C, D, I, the J of 100% steam-treated after 4 hours.Assessing terms is with example 9.Evaluation result sees Table 6.
Example 11
Contain RE(OH)
3Or RE
2O
3The activity stability of USY type molecular sieve catalyst approach conventional REY type molecular sieve catalyst, be better than conventional USY type molecular sieve catalyst.
Through 800 ℃, 100% water vapor respectively catalyzer C, I, the J of pre-treatment after 4,8,12,14.5 hours on pulse micro-inverse, carry out activity assessment respectively.Assessing terms is with example 9.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(OH)
3The active downtrending of USY type molecular sieve catalyst C.Contain RE
2O
3The active downtrending and the curve (2) of USY type molecular sieve catalyst similar.
The different amplitudes of each catalyst activity reduction as can be seen from Fig. 2: the activity stability of molecular sieve catalyst provided by the present invention approaches conventional REY type molecular sieve catalyst.
Example 12
Contain RE(OH)
3Or RE
2O
3USY type molecular sieve catalyst have the characteristic that anti-sodium pollutes.
(amount to and contain Na sodium content is identical
2O0.06%) contain RE(OH)
3USY type molecular sieve catalyst C and conventional USY type molecular sieve catalyst I use pickling process respectively
*Make it contain the sodium amount and increase by 0.5%, 1.0%, 1.5% on the original basis.The forward and backward catalyst sample of dirty sodium carries out activity assessment respectively through 800 ℃, 100% steam-treated on pulse micro-inverse after 4 hours.Assessing terms is with example 9.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) are represented sodium content and catalyst activity reservation percentage ratio on catalyzer C and the catalyst I respectively
The relation of ((cracking activity behind the catalyst contamination sodium)/(cracking activity before the catalyst contamination sodium) * 100%).Contain RE
2O
3USY type molecular sieve catalyst anti-sodium pollutant performance similarly.
As can be seen from Figure 3: the anti-sodium pollutant performance of molecular sieve catalyst provided by the present invention is better than conventional USY type molecular sieve catalyst, and when the contamination level of sodium on the catalyzer reached 1.5%, 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 example weight
1/
2NaCl aqueous solution thorough mixing, then 120 ℃ down oven dry promptly get the catalyst samples of sodium pollution.
Example 13
Contain RE(OH)
3Or RE
2O
3The anti-pollution of vanadium performance of USY type molecular sieve catalyst be better than conventional USY type molecular sieve catalyst.
To contain RE(OH)
3USY 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 9, and evaluation result keeps percentage ratio (implication is with example 12) 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 7.Contain RE
2O
3USY type molecular sieve catalyst anti-pollution of vanadium performance similarly.
Claims (6)
1, a kind ofly be used for molecular sieve catalyst cracking hydrocarbon, that contain rare earth, it is characterized in that:
(a) it is an active ingredient with 5～40% the USY type molecular sieve that contains rare earth oxide, is aided with 95～60% semi-synthetic carrier and constitutes;
(b) rare earth in the USY type molecular sieve is all with RE (OH)
3Or RE
2O
3State exists, and the exchangeable cation position is by Na
+Or H
+Occupy, the similar conventional USY type molecular sieve of its X light powder diffraction spectrogram, but in 2 θ angles be have on 27～29 ° of positions a disperse, RE (OH)
3Or RE
2O
3Characteristic peak;
(c) the USY type molecular sieve that contains rare earth oxide can make by following step:
(1) with NH
4OH or other alkali are with 3.0～4.0: the RECl that mixes of the amount ratio of 1 (molecular ratio) and any composition
3Solution reacts and makes gluey RE (OH)
3
(2) gluey RE (OH)
3After filtration, the washing after, be evenly dispersed in the USY type molecular sieve pulp made from any method RE (OH)
3Consumption should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.11～1.50;
(d) the USY type molecular sieve that contains rare earth oxide also can make by following step: the mixing RE that will make with any method
2O
3After grinding fully, be evenly dispersed in the USY type molecular sieve pulp made from any method RE
2O
3Consumption should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.11～1.50.
2,, it is characterized in that said mixing RECl in (c) (1) according to the described catalyzer of claim 1
3Solution preferably La content is not less than 30% rich La earth solution.
3,, it is characterized in that said mixing RE in (d) according to the described catalyzer of claim 1
2O
3Preferably La content is not less than 30% rich La rare earth oxide.
4, according to the described catalyzer of claim 1, it is characterized in that said RE(OH in (c) (2))
3Consumption preferably should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.25～0.55.
5,, it is characterized in that said RE in (d) according to the described catalyzer of claim 1
2O
3Consumption preferably should make contained RE in the molecular sieve
2O
3/ Al
2O
3(molecular ratio) is 0.25～0.55.
6, the described molecular sieve catalyst of claim 1 is used to comprise catalytic cracking, the hydrocracking of the high heavy oil of heavy oil, particularly sodium content at interior hydro carbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86107598.6A CN1005386B (en) | 1986-12-06 | 1986-12-06 | Super stable y-type molecular sieve cracking catalyst containing rare earths oxidate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86107598.6A CN1005386B (en) | 1986-12-06 | 1986-12-06 | Super stable y-type molecular sieve cracking catalyst containing rare earths oxidate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86107598A true CN86107598A (en) | 1988-06-22 |
| CN1005386B CN1005386B (en) | 1989-10-11 |
Family
ID=4803605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86107598.6A Expired CN1005386B (en) | 1986-12-06 | 1986-12-06 | Super stable y-type molecular sieve cracking catalyst containing rare earths oxidate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005386B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480408A (en) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | Rare earth-containing diesel fuel distillate oil hydrogenation catalyst, preparation and application thereof |
| US9611432B2 (en) | 2009-06-25 | 2017-04-04 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst having a higher selectivity, processing method and use thereof |
-
1986
- 1986-12-06 CN CN86107598.6A patent/CN1005386B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9611432B2 (en) | 2009-06-25 | 2017-04-04 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst having a higher selectivity, processing method and use thereof |
| CN103480408A (en) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | Rare earth-containing diesel fuel distillate oil hydrogenation catalyst, preparation and application thereof |
| CN103480408B (en) * | 2012-06-13 | 2016-01-20 | 中国石油天然气股份有限公司 | A kind of diesel oil distillate oil hydrogenation catalysts containing rare earth and Synthesis and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005386B (en) | 1989-10-11 |
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