CN1186105A - Catalyst containing modified kaoling for cracking hydrocarbons - Google Patents
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- CN1186105A CN1186105A CN96114116A CN96114116A CN1186105A CN 1186105 A CN1186105 A CN 1186105A CN 96114116 A CN96114116 A CN 96114116A CN 96114116 A CN96114116 A CN 96114116A CN 1186105 A CN1186105 A CN 1186105A
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Abstract
A catalyst containing modified kaolin for cracking hydrocarbons contains particle A (10-25%) and existing cracking catalyst particle B (75-90%). Said particle A contains rare-earth/alkali-earth metal oxide whose main component is cerium oxide (10-20%), acid extracted metakaolin (10-95%), zeolite/molecular sieve (0-40%), kaolin (0-50%) and alkaline sol of aluminium chloride (0-15%). When vanadium content is higher, said catalyst can effectively fixate it by generating rare-earth vanadate phase and vanadium-mullite phase. Its advantages are excellent creacking performance and V pollution resistance up to 8000-10000 PPm.
Description
The present invention relates to a kind of modified kaoling for cracking hydrocarbons catalyzer that contains, when the stock oil of the high vanadium charging of processing, they have shown good cracking performance, have greatly improved the coke and the dry gas selectivity of catalyzer, international Patent classificating number C10G47/00.
In recent years because global range crude oil heaviness, poor qualityization day by day seriously and the raising year by year of catalytic cracking process intermingled dregs ratio example, the metallic pollution inactivation problem of cracking catalyst is very outstanding.Pollution metal mainly refers to nickel and the vanadium species in the stock oil.In catalytic cracking process, these metal species decompose and are deposited on the catalyzer.Under regeneration superheated vapor condition, vanadium species can be transformed into volatilizable vanadic acid, and migrates in catalyzer zeolite structured, destroys skeleton structure of zeolite, thereby reduces the cracking activity of catalyzer, causes residual oil processing total cost to increase.
At the problems referred to above, reported that some suppress the method for catalyzer vanadiumism in the catalytic cracking process.Early discovery adds stanniferous liquid metal passivator in stock oil, can stop the organic vanadium species in the stock oil to deposit to (Oil ﹠amp on the catalyzer; Z Gas J., 1984,82 (29), 127); Adopt the vanadium on the thiophosphoric acid tin passivation cracking catalyst among the USP4397767, improved gasoline selective.Found afterwards basic specie such as rare earth oxide, magnesium oxide, titanium oxide have suppress the vanadiumism effect preferably after, in addition extensive utilization.Among the USP 4515683 lanthanum is deposited on the cracking catalyst with non-ionic form, has played certain anti-vanadium effect; Utilize magnesium oxide (as sepiolite) to reduce the influence of vanadium among the USP 4549548; Among the USP 4704375 with passivator that to contain phosphoric acid salt or the stable sharp titanium masonry of sulfuric acid be vanadium.In addition, also reported the anti-vanadium technology of some carriers.Use kaolin and white clouds masonry carrier among the USP 4707461; Use aluminum oxide and rare earth oxide as carrier among the EP 350280; Among the CN 1067679A, at r-Al
2O
3Upload alkaline-earth metal and/or thulium.These methods have all shown certain anti-vanadium effect, but when having a large amount of vanadium on the catalyzer, its anti-vanadium performance is restricted.
USP 4843052, prepared the extractive metakaolin matrix of a kind of acid among the USP 5248642, stronger anti-vanadium, the effect of nickel poisoning have been shown, during but the rare earth that this patent is selected for use is formed mainly based on lanthanum, and the oxide content that requires lanthanum and neodymium is greater than 40%, domestic rare earth is formed and is difficult to reach above-mentioned requirements, thereby is restricted in utilization.
On the prior art basis, the object of the present invention is to provide a kind of hydrocarbon cracking catalyzer with good inhibition pollution of vanadium performance, especially when high vanadium charging, show extremely strong cracking activity stability, improve the coke and the dry gas selectivity of catalyzer simultaneously.Can expect that its anti-vanadium ability reaches 8000～10000ppm.
Unless stated otherwise, composition that the present invention relates to and proportioning are all represented (calculating with butt) with weight percentage.
Fig. 1 be catalyzer 10# of the present invention and 11# sample through 800 ℃, the X-ray powder diffraction figure after 100% steam is handled.
Present invention includes composition and the manufacture method of hydrocarbon cracking catalyzer. Its composition comprises: 5-35%, preferably the particle I of 10-25%; I is by 0-30%, the preferably rare earth of 10-20% and alkaline earth oxide, 10-95%, preferably sour extracting metakaolin and/or the 0-40% of 50-90%, zeolite/molecular sieve of 20-35% preferably, the aluminium chloride colloidal sol of 0～50% protokaolin, 0-15% forms, with 95～65%, the existing Cracking catalyst particle II of 90-75% preferably.
Described rare earth oxide has independently X-ray powder diffraction phase (it is characterized in that 2 θ at 28-29 °, 47-48 ° has respectively a broad peak) in particle I, and the mixed rear earth of selecting, and has following composition, sees Table 1
Table 1 mixed rear earth is formed La
2O
3% 24.9CeO
2% 50.7Pr
8O
11% 6.4Nd
2O
3% 14.0 other, % 4.0
Described sour extracting metakaolin preparation method sees that USP 4843052 (being hereby incorporated by) hydrous kaolin is through 300-900 ℃, after the roasting at least one minute, obtain metakaolin, metakaolin and hydrochloric acid are in molar ratio greater than carrying out back flow reaction at 1: 1.5, time 1-20 hour, promptly obtain sour extracting metakaolin, its mole consists of 0.8～1.0Al
2O
32SiO
2, pore volume is greater than 0.14 milliliter/gram, and specific surface is greater than 100 meters
3/ gram.
Described zeolite/molecular sieve is X type zeolite, y-type zeolite, L zeolite, ZSM zeolite, mordenite, β zeolite, aluminum phosphate zeolite, MCM-41S molecular sieve (seeing WO 91/11390), preferably y-type zeolite, or the above-mentioned zeolite/molecular sieve of process physics or chemical process modification.
Described cracking catalyst particle II is existing complete synthesis or semi-synthetic cracking catalyst particle.Cracking catalyst can contain above-mentioned one or more zeolite/molecular sieve mixture, one or more are selected from the inorganic oxide of silicon oxide, aluminum oxide, magnesium oxide, aluminum phosphate, and wherein semi-synthetic cracking catalyst comprises that also one or more are selected from kaolin, halloysite, polynite, sepiolite and diatomite and/or crosslinked laminated clay.
The size of described granules of catalyst I and distribution and particle II are complementary, particle diameter 5-200 micron, and preferably the percent by volume of 45.8-111.0 micron is greater than 50%.
The modified kaoling for cracking hydrocarbons catalyzer that contains provided by the invention can be prepared by following step:
(1) carries out thorough mixing, slurry solid content 20-45% by the sour extracting metakaolin of above-mentioned UPS 4843052 preparations, and by required proportioning and re chloride, chemical pure magnesium oxide/calcium oxide, protokaolin, aluminium colloidal sol, zeolite/molecular sieve;
(2) above-mentioned slurries are at 120 ℃ of drying and mouldings, and fragmentation is screened to required granular size, or spray into microballoon at 300-350 ℃;
(3) at the 350-650 ℃ of granules of catalyst 0.5-2 that following roasting obtained hour, rare earth chloride was transformed into rare earth oxide, had driven away the chlorion in the granules of catalyst simultaneously; Select as required (4);
(4) granules of catalyst after the roasting as ammonium phosphate washing, drying, obtains finished product through ion-exchange.
By the cracking catalyst that contains modified kaolin of above-mentioned steps preparation can with existing cracking catalyst, carry out fusion as LCS-7, the LC-8 of Lanzhou oil-refining chemical head factory production, mix proportions is 5-35: 95-65, preferably 10-25: 90-75.Also catalyst substance of the present invention can be introduced in existing cracking catalyst preparation.
The cracking catalyst that contains modified kaolin of the present invention has good cracking performance and anti-vanadium ability.Experiment finds that in the presence of high temperature and water vapor, catalyzer of the present invention can form stable cerium vanadate compound with vanadium, thereby vanadium is fixed owing to there is independently rare earth oxide; On the other hand, under very high vanadium concentration, the modified kaolin among the present invention can form tangible vanadium-mullite phase (when no vanadium existed, kaolin was at least through just changing into mullite more than 1000 ℃) under catalytic cracked regenerated condition.Experiment shows that further vanadium has entered on the mullite lattice, wraps up in thereby vanadium has been carried out effective envelope.Therefore, cracking catalyst of the present invention can keep good cracking activity stability when high pollution of vanadium, improved coke and dry gas selectivity, is applicable to the residual oil and the heavy oil catalytic cracking process of high vanadium raw materials oil.Can expect that its anti-vanadium ability reaches 8000-10000ppm.
Below, will the present invention will be further described by embodiment.
Embodiment 1
Prepare sour extracting metakaolin
With 0.3 kilogram/10 minutes 5 kilograms of kaolin fine powders of roasting in converter (character sees Table 2 for numbering YL, Yulin product) of inlet amount, 850 ℃ of temperature, obtain metakaolin at 1 hour residence time.1 kilogram of metakaolin and 0.34 liter of concentrated hydrochloric acid and 2.66 liters of chemical water are mixed, in stainless steel reactor, refluxed 5 hours, promptly get sour extracting metakaolin, remember and make PAL.
Embodiment 2
Cracking catalyst evaluation experiment
The present invention is by the reactivity worth of micro-reactor and fixed bed device evaluation cracking catalyst.Little anti-experiment: the CSA-B type catalyzer evaluation device that little anti-experimental installation is produced for Hua Yang company, aging condition, 800 ℃, 4 hours, 100% water vapor, reaction raw materials oil is the huge port solar oil, 460 ℃ of temperature of reaction, 70 seconds reaction times, catalyzer loading amount 5.0 grams, agent-oil ratio 3.2.Fixture bed experiment: aging condition, 800 ℃, 10 hours, 100% water vapor, reaction raw materials oil is Xinjiang decompression wide fraction oil, 500 ℃ of temperature of reaction, 650 ℃ of regeneration temperatures, weight space velocity 16h
-1, catalyzer loading amount 150 grams, agent-oil ratio 3.75.
By above-mentioned experimental technique, measured the micro-activity of PAL, see Table 3.Compare with the YL original soil, the micro-activity of PAL improves more than 2 times, and pore volume and specific surface have all obtained bigger improvement.Can expect that sour extracting metakaolin will become the active matrix component with strong cracking ability.
Table 2 Yulin Gao Ling goes up character Al
2O
3SiO
2Na
2O K
2O Fe
2O
3D (v, 0.5) D (v, 0.9) % % % % % micron micron 43.29 55.28 0.015 0.277 0.64 3.6 6.7
The physical and chemical performance of metakaolin is taken out in table 3 acid
Specific surface pore volume micro-activity D (v, 0.5) D (v, 0.9) sample rice
2/ gram milliliter/gram % micron micron YL 32 0.119 9.6 3.6 6.7PAL 269 0.188 32.6 3.8 7.1
Embodiment 3
Test required rare earth hydrogen Y molecular sieve, protokaolin, aluminium chlorohydroxide colloidal sol are all taken from Lanzhou oil-refining chemical head factory.
Take by weighing 900 gram rare earth hydrogen Y molecular sieves, 1050 gram protokaolins, 0.96 liter of aluminium chlorohydroxide colloidal sol, (character sees Table 4), 750 gram PAL, 4.5 liters of chemical water, evenly mixed, solid content 34%, slurries are sprayed into microballoon, 500 ℃ of following roastings 50 minutes, obtain catalyst A.Above-mentioned PAL is removed, and the protokaolin add-on is 1800 grams, and other step is constant, obtains contrast medium B.Press embodiment 2 described little anti-experimental techniques, the micro-activity that records A is 75.9%, and the micro-activity of B is 70.1%.As seen compare with contrast medium, the catalyzer micro-activity that contains sour extracting metakaolin improves nearly 6 units.
Table 4 aluminium chlorohydroxide colloidal sol character aluminium Sol A l
2O
3AL/CL (mol ratio) PH density
% kg/liter 951,128 23.27 1.23 3.0 1.347
Embodiment 4-11
Prepare sample 4#-11# by table 5 proportioning, required material and an amount of distilled water are made the homogeneous slurry of solid content 40%, 120 ℃ of drying and mouldings, fragmentation is screened into the 20-40 order, obtains sample 4#-11# in 1.5 hours 540 ℃ of roastings.
The composition proportioning * of table 5 4#-11# sample
Kaolin PAL REHY RECL
3Solution oxide magnesium NH
4VO
3Solution example Ke Keke milliliter gram milliliter 4# 40.0 0 10.0 00 05# 0 40.0 10.0 00 06# 38.1 0 10.0 9.5 0 07# 0 38.1 10.0 9.5 0 08# 37.3 0 10.0 9.5 0.8 09# 0 37.3 10.0 9.6 0.8 010# 8.9 0000 9611# 0 8.9 000 96*RECl3Solution: 200 grams per liters are in rare earth oxide, NH
4VO
3Solution: 0.5% (in vanadium), 10# and 11# sample form slurries, dry forming by proportioning.
Embodiment 12
Getting 5.74 gram ammonium meta-vanadates is dissolved in 3% the aqueous hydrogen peroxide solution and is made into 500 milliliters of solution that contain vanadium 0.5%.With reference to Mitchell method (Ind, Eng, Chem, Prod, Res, Dev, 19,209,1980) with vanadium on the catalyst contamination: earlier 540 ℃ of calcined catalysts 1.5 hours, at room temperature, with an amount of above-mentioned ammonium metavanadate solution immersion catalyzer more than 16 hours, drying is 24 hours under 120 ℃, and 540 ℃ of roastings got final product in 4 hours.
According to aforesaid method, respectively 4#～9# sample is carried out pollution of vanadium, amount is 5000ppm on the vanadium, 10000ppm at 800 ℃, wore out 2 hours under the 100% water vapor condition, measured the retention rate of molecular sieve crystallinity in the catalyzer, saw Table 6.See from table, when identical pollution of vanadium, compare with protokaolin that containing acid, to take out the sample degree of crystallinity retention rate of metakaolin much higher, along with pollution of vanadium increases, this increasing degree is more obvious.Introduce an amount of rare earth in the sample, and/or behind the magnesium oxide, the degree of crystallinity retention rate of all samples increases to some extent all.It shows that sour extracting metakaolin can tolerate pollution of vanadium, plays the effect of molecular sieve structure in the guard catalyst, introduces an amount of rare earth, and/or behind the magnesium oxide, helps anti-vanadium performance to strengthen.
Degree of crystallinity retention rate sample 4# 5# 6# 7# 8# 9#Y crystallization of zeolites 5000ppm 15.3 22.3 21.4 33.6 25.0 37.0 degree retention rate vanadium % 10000ppm 6.1 16.5 11.7 25.5 15.3 29.2 behind table 6 4#～9# sample contamination vanadium
Embodiment 13
10#, 11# sample under 800 ℃, 100% steam aging 2 hours carry out the X-ray powder diffraction material phase analysis then, see Fig. 1.From Fig. 1, see, during sample vanadiumcontent 5%,, all generated vanadium-mullite phase (V-ML) through the steam burin-in process.If no vanadium exists, kaolinite is through just being transformed into the mullite phase more than at least 1000 ℃.But, (C-ML) compares with pure mullite, and diffraction peak 2 θ of the V-ML phase that is generated are to low angle displacement 0.1～0.2 degree.Experiment shows that further the unit cell volume of V-ML phase increases than C-ML, and this is the result that vanadium enters mullite phase lattice.Under identical content of vanadium situation, the formed V-ML of 11# sample that contains sour extracting metakaolin is mutually obviously more than the growing amount of 10#, and this is the major reason that catalyzer of the present invention has good anti-vanadium performance.
Embodiment 14-15
Get routine 1PAL2.13 kilogram, RECl
33.6 rise (200 grams per liter), chemical pure MgO0.015 kilogram, other adds 2.5 kilograms of chemical water, stirs, and solid content 33% is sprayed into microballoon, 500 ℃ of roastings 50 minutes, obtains solid vanadium additive C; In addition, mixture consists of 2.55 kilograms of protokaolins before the spraying, 1.44 kilograms of aluminium colloidal sols, and 4.3 kilograms of chemical water, other step is constant, obtains contrast media D.
Example 16-19
Press the 1cs-7 commercial catalysts 1 that table 7 proportioning is produced Lanzhou oil-refining chemical head factory
#With C or D fusion, get sample 16#-19#.
Table 7 commercial catalysts 1
#The pollution of vanadium laboratory sample commercial catalysts 1 of the solid vanadium additive of fusion
#C D pollution of vanadium degree of crystallinity * structure cell *
Ke Keke ppm retention rate % parameter, nanometer 16# 16 40 5,000 40 2.45117# 16 04 5,000 20 2.44618# 16 40 8,000 22 2.44819# 16 04 8,000 8 2.440*:Y type zeolites
According to embodiment 12 16#～19# is polluted vanadium 5000ppm respectively, 8000ppm, at 800 ℃, 100% water vapor aging 2 hours down.
Experimental result sees Table 7.Can see when identical pollution of vanadium, contain the catalyzer crystallization degree retention rate height of C, structure cell shrinks less, has reduced dealuminization, thereby has protected framework of molecular sieve, illustrates that catalyzer of the present invention has tangible anti-vanadium effect.
Embodiment 20-23
Press the 1c-8 commercial catalysts 2 that table 8 proportioning is produced Lanzhou oil-refining chemical head factory
#Product and C or D fusion obtain 20#～23# sample.
According to embodiment 12 20#～23# is polluted vanadium 4000ppm respectively, 10000ppm, and carry out little anti-experiment by embodiment.Show as table 8, contain catalyzer of the present invention, under identical pollution of vanadium condition, have good active stability, when pollution of vanadium reached 10000ppm, the cracking activity of contrast medium greatly reduced, and the catalyzer that contains C is still kept higher cracking activity.From unit cell parameters, serious dealuminzation phenomenon has taken place in contrast medium (21#, 23#), and the framework of molecular sieve structure is damaged.This shows that solid vanadium additive of the present invention has good provide protection to molecular sieve.
Table 8 commercial catalysts 2
#The pollution of vanadium laboratory sample commercial catalysts 2 of the solid vanadium additive of fusion
#C D pollution of vanadium micro-activity degree of crystallinity * structure cell *
Ke Keke ppm % retention rate, the % constant, nanometer 20# 32 880 4,000 59.5 57 24.3921# 32 808 4,000 31.8 28 24.3122# 32 880 10,000 25.2 30 24.3223# 32 808 10,000 8.2 6 24.20*: refer to y-type zeolite
Embodiment 24-25
With 255 gram commercial catalystss 2
#Catalyzer and 45 gram C thorough mixing are even, obtain catalyzer E, and contrast medium F is by 255 gram commercial catalystss 2
#Catalyzer and the abundant mixing of 45 gram D prepare.By example 12 E and F are polluted vanadium 8000PPM respectively, the physico-chemical property of E and F sees Table 9.
Table 9 E and F pollute the physico-chemical property sample Al behind the vanadium
2O
3Na
2O
3RE
2O
5MgO Cl P unit cell parameters *
% % % % % % nanometer E 43.5 0.64 4.86 0.77 0.10 0.85 2.437F 45.7 0.59 2.57 0.11 0.12 0.83 2.427*: treatment condition: 800 ℃, 10 hours, 100% water vapor refers to Y zeolite.
Carry out the fixed bed qualification test by 2 couples of E of embodiment and F, for the purpose of contrast, also with the uncontaminated commercial catalysts 2 of going up vanadium
#The agent assessment of data lists.With the uncontaminated commercial catalysts 2 of going up vanadium
#Agent is compared, and the transformation efficiency of E and F reduces, and gasoline selective descends.Under the condition of identical vanadium (8000ppm), E compares with F on polluting, and the transformation efficiency of E and gasoline yield are obviously much higher, and the heavy oil productive rate descends, and simultaneously, the selectivity of dry gas and coke decreases.This shows, under higher pollution of vanadium situation, contains cracking catalyst of the present invention and still has higher cracking activity (transformation efficiency), has improved dry gas and coke selectivity in the product simultaneously.
Table 10 E and the qualification test of F fixed bed
* commercial catalysts 2
#The uncontaminated vanadium of going up of agent
| Catalyzer | Commercial catalysts 2 #*????E??????F | |
| Produce dry gas product rich gas and divide gasoline cloth diesel oil, heavy oil m% coke | ????2.1??????????2.5????2.3 ????24.4?????????18.6???14.1 ????50.1?????????32.6???18.7 ????12.2?????????24.0???32.0 ????7.4??????????16.5???27.9 ????3.8??????????5.8????5.0 | |
| Change＞220 ℃ of change rate m%＞330 ℃ | ????80.4?????????59.5???40.1 ????92.6?????????83.5???72.1 | |
| Selectivity | Dry gas/transformation efficiency (＞220 ℃), * 10 2Coke/transformation efficiency (＞220 ℃), * 10 2Gasoline/transformation efficiency (＞220 ℃) | ????2.61?????????4.20????5.74 ????4.73?????????9.75????12.47 ????0.623????????0.548???0.466 |
Claims (18)
1. hydrocarbon cracking catalyzer, it is characterized in that forming and comprise: the particle I of 5-35%, and/or the existing cracking catalyst particle II of 95-65%, wherein particle I is made up of rare earth oxide/alkaline earth metal oxide of 0-30%, the sour extracting metakaolin of 10-95%, zeolite/molecular sieve of 0-40%, the protokaolin of 0-50% and the aluminium chlorohydroxide colloidal sol of 0-15%.
2. according to the described catalyzer of claim 1, it is characterized in that particle I contains rare earth oxide/alkaline earth metal oxide of 10-20%, the sour extracting metakaolin of 50-90%.
3. according to the described catalyzer of claim 1, it is characterized in that the rare earth oxide among the particle I has independently X-ray powder diffraction thing phase (2 θ are at 28～29 °, and 47～48 ° have a broad peak respectively), and cerium oxide content is not less than 40% in the rare earth composition.
4. according to the described catalyzer of claim 1, it is characterized in that containing particle I10-25%, particle II90-75%.
5. according to the described catalyzer of claim 1, it is characterized in that sour extracting metakaolin mole composition 0.8～1.0Al
2O
32SiO
2, pore volume is greater than 0.14 milliliter/gram, or specific surface is greater than 100 meters
2/ gram.
6. according to the described catalyzer of claim 1, it is characterized in that alkaline earth metal compound is magnesium oxide or calcium oxide.
7. according to the described catalyzer of claim 1, it is characterized in that size and the distribution of particle I and particle II is complementary, particle diameter is the 5-200 micron, and the percent by volume of 45.8-111.0 micron is greater than 50%.
8. according to the described catalyzer of claim 1, it is characterized in that described cracking catalyst particle II is existing complete synthesis or semi-synthetic cracking catalyst.
9. by the described catalyzer of claim 8, it is characterized in that described complete synthesis cracking catalyst contains zeolite/molecular sieve component, one or more select the inorganic oxide in silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, the aluminum phosphate for use.
10. according to the described catalyzer of claim 8, it is characterized in that described semi-synthetic cracking catalyst except that containing the described component of claim 9, comprise that also one or more select kaolin, halloysite, polynite, sepiolite, diatomite clay and/or crosslinked laminated clay for use.
11., it is characterized in that described zeolite/molecular screening is from X type zeolite, y-type zeolite, zeolite L, ZSM zeolite, mordenite, β zeolite, aluminum phosphate zeolite, MCM-41S molecular sieve according to claim 9 or 10 described catalyzer.
12. make the hydrocarbon cracking catalyzer method:
1) the sour extracting metakaolin of preparation;
2) form mixed serum with various function ingredients;
3) spraying drying is shaped;
4) 300-700 ℃ of roasting, select 5 as required;
5) particle process ion-exchange after the roasting is as ammonium phosphate washing, drying.
13., it is characterized in that containing 0-15% aluminium chlorohydroxide colloidal sol, 0-30% rare earth/alkaline earth metal oxide, the sour extracting metakaolin of 10-95% in the mixed slurries according to the manufacture method of the described catalyzer of claim 12;
14., it is characterized in that aluminium chlorohydroxide colloidal sol consists of Al in the mixed slurries according to the manufacture method of the described catalyzer of claim 13
2+m(OH)
3mCl
6, m=4～12 wherein.
15., it is characterized in that mixed slurries contain the 0-50% protokaolin according to the manufacture method of the described catalyzer of claim 12.
16., it is characterized in that mixed slurries middle-weight rare earths oxide compound oxidation-containing cerium is not less than 40% according to the manufacture method of the described catalyzer of claim 13.
17., it is characterized in that alkaline earth metal oxide is magnesium oxide or calcium oxide in the mixed slurries according to the manufacture method of the described catalyzer of claim 13.
18., it is characterized in that containing the described zeolite/molecular sieve of claim 11 in the mixed slurries according to the manufacture method of the described catalyzer of claim 12.
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| CN101433865B (en) * | 2007-11-15 | 2010-12-22 | 中国石油化工股份有限公司 | Residual oil hydrocatalyst carrier and preparation method thereof |
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| CN1020281C (en) * | 1989-12-13 | 1993-04-14 | 中国石油化工总公司石油化工科学研究院 | Cracking catalyst |
| US5248642A (en) * | 1992-05-01 | 1993-09-28 | W. R. Grace & Co.-Conn. | Catalytic cracking catalysts and additives |
| US5364516A (en) * | 1992-05-01 | 1994-11-15 | W. R. Grace & Co.-Conn. | Catalytic cracking catalysts and additives |
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1996
- 1996-12-24 CN CN96114116A patent/CN1064072C/en not_active Expired - Fee Related
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