CN1334318A - Process for preparing full-clay high octane number catalytic cracking catalyst - Google Patents
Process for preparing full-clay high octane number catalytic cracking catalyst Download PDFInfo
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- CN1334318A CN1334318A CN 00122006 CN00122006A CN1334318A CN 1334318 A CN1334318 A CN 1334318A CN 00122006 CN00122006 CN 00122006 CN 00122006 A CN00122006 A CN 00122006A CN 1334318 A CN1334318 A CN 1334318A
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Abstract
A high octane number fluidizing catalytic cracking catalyst is prepared from gaolin as main raw material through pulping gaolin, spray granulating, high-temp calcining of partial microspheres, low-temp calcining of the rest, proportional mixing, hydrothermal crystallizing, ion exchange and hydrothermal modification for high stability.
Description
The invention belongs to the cracking hydrocarbon oil field, saying so a kind of more specifically is the method that main raw material prepares the full-clay high octane number fluidized catalytic cracking catalyst with kaolin.
The conventional preparation method of fluid catalytic cracking (FCC) catalyzer is that active constituent (as Y zeolite) and matrix component (as kaolin) are mixed the back is binding agent with silicate, aluminium salt or silico-aluminate, after spray shaping is the microballoon of about 40～100 μ m, prepare finished catalyst through a series of aftertreatments again, binding agent also is one of matrix component simultaneously.The general preventing from heavy metal pollution ability of the catalyzer that makes like this is relatively poor.The seventies USP3506594,3503900,3647718 to have proposed be the technology that raw material prepares the in-situ crystallization zeolite of active constituent and matrix simultaneously with kaolin, the FCC catalyzer that obtains with the in-situ crystallization method is called the kaolin type catalyzer, also claims full clay catalyst.This class catalyzer has very strong preventing from heavy metal pollution ability, the activity index height, and hydrothermal stability, structural stability are good.
General metakaolin (hereinafter to be referred as the inclined to one side soil) microballoon that uses during the full carclazyte FCC catalyzer of early stage preparation.The technology of preparing that contains faujusite cracking catalyst (particle size range 50-80 μ m) that UK1271450 describes is that kaolin microsphere becomes metakaolin in roasting below 704 ℃, again with the synthetic Y zeolite of reaction such as water glass; What US3377006 described is to synthesize Y zeolite with special thin native partially powder.The crystallization product mesolite content height of native partially microballoon preparation, but the low and intensity difference of zeolite silica alumina ratio.
USP3367886,3367887,3506594,3647718,3657154,3663165, the silica alumina ratio of Y zeolite is higher in the whole uses of the 3932268T proposition in-situ crystallization product that high-temperature roasting soil (hereinafter to be referred as high soil) prepares more than 900 ℃, but degree of crystallinity is lower than 30%, generally between 20-30%.
USP3657154 has announced and has added fine powder soil partially that in the crystallization system cause the tenderly white powder of ex situ crystallization to increase, the crystallization yield reduces, the crystallization product filtration difficulty; EP192453 gets native partially microballoon with the part atomized microball 720 ℃ of roastings, another part gets high native microballoon in roasting more than 900 ℃, for improving zeolite content, adopt fractional crystallization, but example shows, the degree of crystallinity of crystallization product and silica alumina ratio are not high, and the NaY zeolite content in the microballoon is 19%, silica alumina ratio (SiO
2/ Al
2O
3Mol ratio) be about 4.4.
The technology that contains inclined to one side soil and high soil and the synthetic high zeolite content crystallization product of crystal seed in same microballoon has simultaneously been described at US4493902, crystallization product degree of crystallinity is higher than 40%, and EP194101 has described the crystallization product that the USP4493902 technology is obtained and carried out ion-exchange and calcination process, the preparation content of rare earth catalyzer different with the Y zeolite lattice constant.But very high to the used ingredient requirement of spray shaping in the USP4493902 technology: use high native Satone No2 of super-refinement and super-refinement original soil ASP～600, this ultra-fine soil costs an arm and a leg, and is difficult on the market buying.
EP369629 has described and has adopted the method that improves the high soil of fine powder in the spray slurry to increase parent microballoon pore volume, increase by pore volume improves microballoon mesolite content, can make crystallization product degree of crystallinity up to 70%, but ultra-fine powdery kaolin costs an arm and a leg, and contain in the atomized microball in a large number and passed through kaolin roasting, bad adhesion, make the resistance to abrasion of microballoon poor.
The objective of the invention is to overcome the shortcoming of prior art, adopting the thicker and inexpensive kaolin of granularity is raw material, prepares the crystallization product microballoon of zeolite content at 25-35%, and crystallization product is handled through modification, it is good to prepare use properties, the FCC catalyzer that gasoline octane rating is high.
Realize technical scheme of the present invention: protokaolin is added water make the slurries that solid content is 20-55%, in slurries, add dispersion agent and caking agent, spray drying forming is the microballoon of 20-111 μ m, a part of microballoon is obtained high-temperature roasting microballoon (being called for short high soil) at 940-1000 ℃ of roasting 1-3h, another part microballoon becomes metakaolin (being called for short soil partially) at 700-900 ℃ of roasting 1-3h, after two kinds of roastings soil balls are mixed by a certain percentage, add water glass, directed agents, sodium hydroxide solution, chemical water, in 90～95 ℃ of crystallization 16-36h, remove by filter mother liquor, it is below 10.5 that filter cake is washed till PH with deionized water, obtain a kind of crystallization product of the NaY of comprising molecular sieve after the drying, crystallization product is carried out hydro-thermal after twice exchange of ammonium sulfate super steady, adopt the rare earth chloride exchange then successively, roasting, method of modifying such as ammonium phosphate exchange are prepared high-octane rating FCC catalyzer.
Concrete preparation method is as follows:
One, the preparation of crystallization product microballoon
Preparation process is followed successively by:
1. the protokaolin about meso-position radius 3 μ m is added water and make the slurries that solid content is 30-50%, and add paucidisperse agent and binding agent.Spray-dried 20-111 μ m, the most parent microballoon of being shaped at 40-100 μ m.700-800 ℃ of spray tower inlet temperature, temperature out 120-300 ℃.
2. the part parent makes kaolin microsphere change into based on spinel and with the high-temperature roasting microballoon (being called for short high soil) of a small amount of mullite through the heat release phase transformation 940-1000 ℃ of roasting, and another part parent microballoon makes it to change into metakaolin microballoon (being called for short native partially) 700-900 ℃ of roasting.
3. drop in the reactor successively water glass, deionized water, sodium hydroxide, directed agents, high soil, inclined to one side soil in proportion, under whipped state in 90-95 ℃ of hydrothermal crystallizing 16-36 hour, remove by filter mother liquor, the filter cake deionized water wash, drop to below 10.5 until the pH of washings, filter and promptly get the crystallization product microballoon.
The described protokaolin of step 1 comprises soft kaolin, hard kaolinite, coal gangue, its meso-position radius is 2.5-3.5 μ m, and crystal kaolinite content will be higher than 80%, quartz is lower than 1%, ferric oxide is lower than 1.7%, sodium oxide and potassium oxide sum are lower than 0.5%.Described dispersion agent and caking agent comprise water glass, sodium hydroxide, trisodium phosphate, Sodium hexametaphosphate 99 etc., and its add-on is the 2-4% of kaolin quality.
The described Gao Tuzhong of step 2 contains the mullite of 6-20%, is preferably 8-16%, and abrasion index is less than 4%; Do not contain mullite in the soil partially.Its abrasion index is less than 4%.
The described water glass of step 3, deionized water, sodium hydroxide, directed agents, high soil, the ratio of soil is partially: native=10: the 0-4: 6 of high soil/partially; Liquid phase SiO
2/ (high soil+native partially)=0.4-2.0.It consists of described directed agents: (14-16) SiO
2: (0.7-1.3) Al
2O
3: (14-16) Na
2O: (300-330) H
2O (mol ratio), naoh concentration are 14-18%.
Two, Preparation of catalysts
1. one hand over: adding crystallization product and ammonium sulfate successively, is 3.0-3.5 at pH value, and temperature is 90-94 ℃ of exchange 0.5-1 hour down, the microballoon after the exchange after filtration, wash, refilter, one hand over material, (NH
4)
2SO
4/ crystallization product=0.2-0.5.
2. two hand over: hand over one and expect that the pH value is 3.0-3.5 with the ammonium sulfate exchange, temperature 90-94 ℃, time 0.5-1 hour, filter, wash, refilter the exchange product, get two and hand over material, (NH
4)
2SO
4/ one hands over material=0.2-0.5.
3. a roasting: hand over material under 550-600 ℃, the flowing water atmosphere of 50-100% roasting 1-2 hour with two, a roasting material.
4. three hand over: a roasting material exchanges 0.5-1 hour with mixed chlorinated rare earth again under pH=3.5-4.0,90-94 ℃ condition, filter, wash, refilter the exchange product, gets three and hands over material.RE
2O
3/ one roasting material=0.5-3.5%.
5. two roastings: hand over the filter cake of material to get two roasting material at 600-650 ℃ of roasting 1-2 hour with three.
6. four hand over: the two roasting material condition of 1 exchange set by step replenish exchange once with ammonium phosphate and ammonium sulfate, the exchange product after filtration, after the washing, filtration, drying finished catalyst, described ammonium phosphate add-on is the 5-10% of two roasting material, and the ammonium sulfate add-on is the 20-50% of two roasting material.
Major advantage of the present invention and effect:
The present invention can prepare abrasion index less crystallization product microballoon and catalyzer with the feed kaolin of thick (the granularity meso-position radius of laser particle analyzer method test is about 3 μ m); Preparing the NaY zeolite content with technical process provided by the invention is that 25-35%, the overwhelming majority are at the crystallization product microballoon more than 30%; Available crystallization product microballoon provided by the invention prepares that the preventing from heavy metal pollution ability is strong, heat and the good all-white clay catalyst for fluid catalytic cracking of use properties such as hydrothermal stability height, gasoline octane rating height.
Further specify characteristics of the present invention with example below.
Catalyzer use properties evaluation method in the example: 1. activity: the micro fixed-bed reactor method, before the test earlier with live catalyst aging 4 hours of 800 ℃, 100% water vapour.2. selectivity: fixed fluidized bed method, before measuring earlier with live catalyst at 800 ℃ with aging 10 hours of 100% water vapour.Estimate used stock oil character and see Table 2, the intermingled dregs ratio example is 30%.500 ℃ of temperature of reaction, catalystoil ratio are 3.75, catalyzer Intake Quantity 150g, oil inlet quantity 40g, air speed 16h
-1Analysis and assessment method related in the example see table 1 for details.
Example 1-example 3 is described the preparation of crystallization product microballoon.
Example 1
With 10Kg (butt) meso-position radius is that the protokaolin of 3.1 μ m adds water to make solid content be 35% slurries, and adds a small amount of water glass as dispersion agent, and spray shaping is a microballoon, the parent microballoon of 8.5Kg.Get the 940 ℃ of roastings in muffle furnace of 5Kg parent microballoon and got high native microballoon 4.5Kg in 3 hours, the 870 ℃ of roastings in muffle furnace of the parent microballoon of residue 3.5Kg got native partially microballoon 3Kg in 1 hour.Gao Tuzhong contains the mullite about 8%, and soil does not contain mullite partially.Under whipped state, successively water glass (is contained 19.84% SiO
2, 6.98% Na
2O) 1800ml, alkali lye (containing 14% NaOH) 670ml, guiding agent for zeolite (contain 11.65% SiO
2, 1.32% Al
2O
3, 12.89% Na
2O) 87.2ml, deionized water 318ml, high native 600g, native partially 400g drop in the stainless steel reactor, are warmed up to 90 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, dry cake obtain crystallization product microballoon crystallization product.Measure through X-ray diffraction, crystallization product contains 32% NaY zeolite, and zeolite silica alumina ratio (mol ratio) is 5.3.
Example 2
All reaction raw materials are with example 1, wherein the roasting condition of high soil is 990 ℃, 1 hour, under agitation successively water glass 4800ml, alkali lye 540ml, directed agents 240ml, high native 300g, native partially 300g are dropped in the stainless steel reactor, be warming up to 90 ℃ and thermostatic crystallization 20 hours.X-ray diffraction is measured crystallization product and is contained 35% NaY zeolite, and the zeolite silica alumina ratio is 4.0.
Example 3
All reaction raw materials are with example 1, wherein the roasting condition of soil is 730 ℃, 3 hours partially, under agitation successively water glass 4200ml, alkali lye 500ml, directed agents 120ml, high native 160g, native partially 240g are dropped into glass reactor, 90 ℃ of crystallization after 32 hours, the crystallization product crystallization product contains 27% NaY zeolite after measured, and the zeolite silica alumina ratio is 4.8.
Example 4-example 6 is described Preparation of catalysts
Example 4
(1) one hands over: add deionized water 3Kg in the stainless steel still, stir and drop into the crystallization product crystallization product 600g and the ammonium sulfate (ammonium sulfate/crystallization product=0.50) of example 1 preparation down, exchange is 1 hour under pH=3.0-3.5,90 ℃ of conditions, removes by filter mother liquor, filter cake gets one with deionized water wash and hands over material.
(2) two hand over: the same friendship of switching method, ammonium sulfate/crystallization product=0.30
(3) one roastings: hand over material roasting 2 hours under 550 ℃, the flowing water atmosphere of 50-100% with two, a roasting material.
(4) three hand over: one hands over material (adding the 3Kg water slurryization) again with containing 19.2g RECl
31 (RE of mixed chlorinated rare earth solution exchange
2O
3/ crystallization product weight ratio is 0.035), exchange process is the same, exchange pH=3.5-4.0, exchange product after filtration, wash, three hand over material.
(5) hand over material to place stainless steel to open wide vessel with three, the about 3cm of material thickness, 600 ℃ of roastings 2 hours, naturally cooling promptly gets one and bakes and expect.
(6) four hand over: two roasting material are replenished exchange by (1) described method with ammonium sulfate (ammonium sulfate/two roasting material=0.20) and ammonium phosphate (ammonium phosphate/two roasting material=0.08).The exchange product after filtration, after the washing, filtration, drying finished catalyst A.
Example 5
Prepare catalyzer with the crystallization product of example 3 methods preparations by the method for example 5, wherein three RE when handing over
2O
3The ammonium phosphate when ratio of/crystallization product is 0.07, four friendship/two roasting material=0.10 gets catalyst B.
Physico-chemical property and the selectivity of catalyst A, B are listed in table 3, and compare with full carclazyte industrial agent LB-1 of the same type simultaneously, and experimental result sees Table 3.
Example 6
This example is investigated the preventing from heavy metal pollution performance and the hydrothermal stability of the catalyzer of example 5 methods preparation.The catalyzer of example 5 methods preparation is polluted with nickelous nitrate and inclined to one side alum acid ammonium, method be with the analytical pure nickelous nitrate and partially alum acid ammonium be mixed with 2% and 1% solution respectively, quantitatively be impregnated into Ni and V on the catalyzer according to certain pollution level with pickling process, after 120 ℃ of dryings 24 hours, in 530 ℃ of roastings 4 hours.Catalyzer after the pollution is measured active (seeing Table 4) through 800 ℃, 100% steam after aging 4 hours.
From table 3 result as seen, compare with contrast medium, the catalyzer of preparation of the present invention because the molecular sieve content height, and has carried out hydro-thermal super steady and phosphorus modification to catalyzer, makes catalyzer keeping under the prerequisite of higher conversion, has improved gasoline octane rating.In addition, from table 4 result as seen, the catalyzer of the present invention's preparation has kept the strong advantage of full clay catalyst preventing from heavy metal pollution ability simultaneously, is more suitable for the requirement of modern petroleum refining industry to catalyzer.All in all, the catalyzer of the present invention's preparation is the FCC catalyzer that a kind of preventing from heavy metal ability is strong, gasoline octane rating is high, reactivity worth is good.
Main analysis and assessment method that table 1 the present invention relates to
| Project | Method | Standard code |
| Na 2O | Flare photometer | Q/SH018.0144 |
| RE 2O 3 | Colorimetry | Q/LZJ.0023 |
| ?P | Phosphorus molybdenum colorimetry | Q/SH018.0222 |
| Lattice constant | The X-ray diffraction method | ASTM?D3942 |
| Abrasion index | The gas lift method | Q/SH018.0833 |
| Pore volume | The tetrachloro carbon adsorption | Q/SH018.838 |
| Specific surface | The thermal desorption chromatography | Q/LZJ.0013 |
| Catalyst activity | The microreactor method | Q/SH0180846 |
| Catalyst selectivity | Fixed fluidized bed method | Q/LZJ.0009 |
| Gasoline octane rating | Chromatography | Q/SH018.0133 |
Table 2 catalyst selectivity is evaluated raw materials used oil nature
| Project | Xinjiang decompression wide fraction wax oil | Xinjiang vacuum residuum |
| Carbon residue m% flash-point ℃ pour point ℃ | ????0.012 ????136 ????38 | ????9.6 ????316 ????/ |
| Ultimate analysis: N m% C m% H m% | ????0.014 ????85.87 ????13.32 | ????0.55 ????86.00 ????12.25 |
| Heavy metal is analyzed Cu ppm Pb ppm Fe ppm Ni ppm V ppm As ppm | ????0.03 ????＜0.1 ????1.55 ????0.14 ????0.04 ????＜0.2 | ????0.073 ????0.20 ????3.22 ????20.8 ????1.90 ????0.87 |
| PONA analysis stable hydrocarbon m% aromatic hydrocarbons m% colloid m% | ????91.2 ????7.7 ????1.1 | ????55.7 ????41.5 ????2.7 |
| Molecular weight M | ????293 | ????/ |
Table 3 catalyzer of the present invention compares with similar industrial contrast medium performance
| Project | Catalyst A | Catalyst B | Contrast medium | |
| Physico-chemical property | RE 2O 3???m％ | 3.2 | ?0.6 | ?4.7 |
| ?Na 2O????m％ | 0.42 | ?0.40 | ?0.43 | |
| ?a 0?×10 -10m | 24.60 | ?24.55 | ?24.70 | |
| Pore volume ml/g | 0.23 | ?0.22 | ?0.22 | |
| Specific surface m 2/g | 396 | ?352 | ?248 | |
| Abrasion index m% | 1.0 | ?1.2 | ?1.0 | |
| Micro-activity *m％ | 76 | ?74 | ?77 | |
| Selectivity * * | Dry gas m% | 2.6 | ?2.1 | ?2.4 |
| Rich gas m% | 22.0 | ?20.5 | ?18.7 | |
| Gasoline m% | 49.0 | ?47.7 | ?45.4 | |
| Diesel oil m% | 13.2 | ?14.8 | ?17.7 | |
| Heavy oil m% | 7.2 | ?8.9 | ?10.0 | |
| Coke m% | 4.6 | ?4.3 | ?4.2 | |
| Transformation efficiency m% | 78.2 | ?74.6 | ?70.7 | |
| ?RON | 91.76 | ?91.91 | ?89.31 | |
| ?MON | 79.70 | ?79.03 | ?78.47 | |
*800 ℃, 4h, 100% steam are aging
*800 ℃, 10h, 100% steam are aging
The hydrothermal stability of table 4 catalyzer and preventing from heavy metal pollution performance
*
| Test group | Catalyzer | (Ni＋V)ppm | Little work, m% |
| ????1 | Catalyst B | ????2000 | ????72 |
| Contrast medium | ????2000 | ????73 | |
| ????2 | Catalyst B | ????4000 | ????70 |
| Contrast medium | ????4000 | ????70 | |
| ????3 | Catalyst B | ????6000 | ????68 |
| Contrast medium | ????6000 | ????67 | |
| ????4 | Catalyst B | ????8000 | ????66 |
| Contrast medium | ????8000 | ????62 | |
| ????5 | Catalyst B | ????10000 | ????64 |
| Contrast medium | ????10000 | ????60 |
*Ni/V=10/1 (atomic ratio)
Claims (7)
1. preparation method who contains the high-octane rating fluidized catalytic cracking catalyst of modified zeolite of Y-type, it is characterized in that the Preparation of catalysts process is: protokaolin is added water make the slurries that solid content is 20-55%, in slurries, add dispersion agent and caking agent, spray drying forming is the microballoon of 20-111 μ m, a part of microballoon is obtained high-temperature roasting microballoon (being called for short high soil) at 940-1000 ℃ of roasting 1-3h, another part microballoon becomes metakaolin (being called for short soil partially) at 700-900 ℃ of roasting 1-3h, with two kinds of roastings soil balls by high soil: native=10: 0-4: after 6 the mixed partially, add water glass, directed agents, sodium hydroxide solution, chemical water, in 90～95 ℃ of crystallization 16-36h, remove by filter mother liquor, it is below 10.5 that filter cake is washed till PH with deionized water, obtain a kind of crystallization product of the NaY of comprising molecular sieve after the drying, crystallization product is super steady through ion modification and hydro-thermal, prepare high-octane rating FCC catalyzer.
2. according to the described method of claim 1, it is characterized in that described protokaolin comprises soft kaolin, hard kaolinite, coal gangue, its meso-position radius is 2.5-3.5 μ m, and crystal kaolinite content will be higher than 80%, ferric oxide is lower than 1.7%, sodium oxide and potassium oxide sum are lower than 0.5%.
3. according to the described method of claim 1, it consists of to it is characterized in that described directed agents: (14-16) SiO
2: (0.7-1.3) Al
2O
3: (14-16) Na
2O: (300-330) H
2O (mol ratio).
4. according to the described method of claim 1, it is characterized in that described naoh concentration is 14-18%.
5. according to the described method of claim 1, in the crystallization product that it is characterized in that making, the NaY zeolite content is 25-35%, zeolite silica alumina ratio 4.0-5.5.
6. according to the described method of claim 1, it is characterized in that ion modification reagent is ammonium sulfate, rare earth chloride, ammonium phosphate.
7. according to the described method of claim 1, it is characterized in that wherein rare earth oxide content is 0.5-3%, sodium oxide is for being not more than 0.5%, and phosphorus content is 0.6-1.2%, and lattice constant is 24.40-24.65 * 10
-10M.
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Cited By (15)
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|---|---|---|---|---|
| US7067449B2 (en) | 2003-03-28 | 2006-06-27 | China Petroleum & Chemical Corporation | Y-zeolite-containing composite material and a process for preparing the same |
| CN1307287C (en) * | 2004-08-31 | 2007-03-28 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalyst |
| CN100429149C (en) * | 2004-11-26 | 2008-10-29 | 中国石油天然气股份有限公司 | Production for synthesizing high-content NaY molecular sieve from kaolin atomized microball |
| CN100450617C (en) * | 2005-10-18 | 2009-01-14 | 中国石油天然气股份有限公司 | A kaolin based compound molecule sieve and preparation method thereof |
| CN101890362A (en) * | 2009-05-19 | 2010-11-24 | 谭志平 | Fluid catalytic cracking catalyst with low coke yield and preparation method thereof |
| CN101940944A (en) * | 2010-06-24 | 2011-01-12 | 神华集团有限责任公司 | Method for preparing formed molecular sieve catalyst, and product obtained by method and application thereof |
| CN102372281A (en) * | 2010-08-25 | 2012-03-14 | 中国石油天然气股份有限公司 | Preparation method of NaY zeolite |
| CN102464333A (en) * | 2010-11-04 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve by in-situ crystallization |
| CN102019197B (en) * | 2009-09-18 | 2012-07-18 | 中国石油天然气股份有限公司 | Method for synthesizing kaolin microsphere in-situ crystallized product containing small crystal grain NaY molecular sieves |
| CN102764670A (en) * | 2012-07-31 | 2012-11-07 | 海南出入境检验检疫局检验检疫技术中心 | In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst |
| CN103058218A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of NaY molecular sieve |
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| CN112108190A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气股份有限公司 | Preparation method of high-activity carrier material |
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| US7067449B2 (en) | 2003-03-28 | 2006-06-27 | China Petroleum & Chemical Corporation | Y-zeolite-containing composite material and a process for preparing the same |
| CN1307287C (en) * | 2004-08-31 | 2007-03-28 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalyst |
| CN100429149C (en) * | 2004-11-26 | 2008-10-29 | 中国石油天然气股份有限公司 | Production for synthesizing high-content NaY molecular sieve from kaolin atomized microball |
| CN100450617C (en) * | 2005-10-18 | 2009-01-14 | 中国石油天然气股份有限公司 | A kaolin based compound molecule sieve and preparation method thereof |
| CN101890362A (en) * | 2009-05-19 | 2010-11-24 | 谭志平 | Fluid catalytic cracking catalyst with low coke yield and preparation method thereof |
| CN102019197B (en) * | 2009-09-18 | 2012-07-18 | 中国石油天然气股份有限公司 | Method for synthesizing kaolin microsphere in-situ crystallized product containing small crystal grain NaY molecular sieves |
| CN101940944A (en) * | 2010-06-24 | 2011-01-12 | 神华集团有限责任公司 | Method for preparing formed molecular sieve catalyst, and product obtained by method and application thereof |
| CN102372281A (en) * | 2010-08-25 | 2012-03-14 | 中国石油天然气股份有限公司 | Preparation method of NaY zeolite |
| CN102372281B (en) * | 2010-08-25 | 2013-07-31 | 中国石油天然气股份有限公司 | Preparation method of NaY zeolite |
| CN102464333A (en) * | 2010-11-04 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve by in-situ crystallization |
| CN102464333B (en) * | 2010-11-04 | 2013-10-16 | 中国石油天然气股份有限公司 | Method for preparing NaY molecular sieve by in-situ crystallization |
| CN103058218B (en) * | 2011-10-21 | 2015-01-21 | 中国石油化工股份有限公司 | Preparation method of NaY molecular sieve |
| CN103058218A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of NaY molecular sieve |
| CN102764670A (en) * | 2012-07-31 | 2012-11-07 | 海南出入境检验检疫局检验检疫技术中心 | In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst |
| CN104028296A (en) * | 2014-05-16 | 2014-09-10 | 茂名市茂群高岭土有限公司 | Kaolinic catalyst prepared by adopting Maoming kaolin |
| CN104888840A (en) * | 2015-01-14 | 2015-09-09 | 任丘市华北石油科林环保有限公司 | Preparation method for high-framework silica-alumina-ratio in-situ crystallization FCC heavy oil transforming auxiliary agent |
| CN112108190A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气股份有限公司 | Preparation method of high-activity carrier material |
| CN112108190B (en) * | 2019-06-21 | 2023-06-30 | 中国石油天然气股份有限公司 | Preparation method of high-activity carrier material |
| CN111908485A (en) * | 2020-07-01 | 2020-11-10 | 湖南聚力催化剂股份有限公司 | Preparation method of Y-type molecular sieve |
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