CN101746778A - Composite material containing double-pore structure Y-type zeolite, and preparation method thereof - Google Patents
Composite material containing double-pore structure Y-type zeolite, and preparation method thereof Download PDFInfo
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- CN101746778A CN101746778A CN 200810227657 CN200810227657A CN101746778A CN 101746778 A CN101746778 A CN 101746778A CN 200810227657 CN200810227657 CN 200810227657 CN 200810227657 A CN200810227657 A CN 200810227657A CN 101746778 A CN101746778 A CN 101746778A
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Abstract
The invention discloses a composite material containing double-pore structure Y-type zeolite, which is characterized in that the composite material contains NaY zeolite and the balance of amorphous matrix; based on the weight of the composite material, the NaY zeolite accounts for 40 to 85 percent; the secondary structure of the composite material is a similar sphere; the similar sphere is formed by staggering and stacking Y-type zeolite generated by crystallization andmetakaolin amorphous intermediates generated during crystal transformation, and has gaps and holes; the sphere also has nest channels inside; the particle size is 3,000 to 25,000 nm; the surface area measured by a BET method is 280 to 800 M<2>/g; the total pore volume is 0.35 to 0.45 ml/g; the pore volume of 1.7 to 300 nm middle/big holes is 0.05 to 0.150 ml/g and accounts for 20 to 35 percent of the total pore volume.
Description
Technical field
The present invention a kind ofly contains double-pore structure y-type zeolite matrix material and preparation method by kaolin in-situ synthetic macrobead, specifically, be that a kind of macrobead that contains y-type zeolite that is made by the former powder in-situ crystallization of kaolin has matrix material of double-pore structure and preparation method thereof.
Background technology
Since USP 3119659 announcements in 1964 were the raw material synthetic zeolite with kaolin, the research of this respect was constantly being carried out always.Early stage work mainly is the zeolite of being devoted to synthetic pure phase, a kind of method with the synthetic y-type zeolite of kaolin is disclosed as USP3574538, the kaolin roasting is become unformed metakaolin, add a certain amount of water glass and sodium hydroxide, make the mol ratio of its silica and desire the approaching of synthetic zeolite, add the directed agents of the heavy % of 0.1-10 then, make the very high Y zeolite of purity after the 60-110 ℃ of crystallization, the mol ratio of its silica is 4.5-5.95.
EP 0209332A2 discloses a kind of method that kaolin raw material crystallization is prepared y-type zeolite under agitation condition, this method makes metakaolin with kaolin 550-925 ℃ of roasting, add sodium source compound and water again, regulate silicon oxide: alumina molar ratio is 2.1-15: 1, water: the mol ratio of sodium oxide is 15-70: 1, under agitation make the reactant crystallization form Y zeolite, can add directed agents in the raw material.The synthetic Y zeolite is median size 3000nm, and NaY purity reaches 97% the powder that is dispersion state.
Employing halloysites such as tall and big dimension prepare Y zeolite [refining of petroleum, 1983, (7): 12-16], this method is made metakaolin with halloysite at 640-660 ℃ of lower roasting temperature, add sodium hydroxide, directed agents and water glass then, 50-60 ℃ aging 1 hour, 98-100 ℃ following crystallization 2-24 hour, the zeolite NaY degree of crystallinity that makes after the drying is greater than 80%, and the mol ratio of silica is greater than 4.5.This zeolite shows hydrothermal stability preferably after with rare earth exchanged.This research is to utilize kaolinic silicon source and aluminium source, the NaY of synthesis of high purity, and adopting stirring in the crystallization process still is the static explanation that do not have.Synthetic product pattern and granular size also undeclared [refining of petroleum, 1986, (2): 41-46].
CN 1334142A becomes to contain the high soil of spinel 940-1000 ℃ of roasting with the former powder of a part of kaolin, another part becomes metakaolin 700-900 ℃ of roasting, then the soil after two kinds of roastings is mixed in proportion, add water glass, directed agents, sodium hydroxide and water again, 90-95 ℃ crystallization 16-36 hour, obtain the molecular sieve that NaY content is 40-90% after the drying.Kaolinic maturing temperature reached 1000 ℃ when this legal system was equipped with molecular sieve, and it is bigger to consume energy.The unreceipted crystallization process of this patent is an immobilized or dynamic, and the explanation of product pattern and granular size is not arranged.In its correlative study [Lanzhou University's graduate degree paper, Liu Honghai, 2006], do not introduce synthesis step in detail yet, the SEM pattern of listed product is similar to conventional gel method, is more homodisperse particle, and the granular size scope is between 500 nanometers-3000 nanometer.
It is raw material that CN 1789127A adopts cheap natural rich aluminium clay, at 700-1100 ℃ of roasting 1-20 hour, the roasting sample is extracted aluminium or silicon is handled by mineral acid or inorganic alkali solution, obtain containing mesoporous clay, crystallization is synthetic again is rich in mesoporous Y zeolite.This research adopts mineral acid or mineral alkali to handle roasting kaolin, though can obtain being rich in mesoporous Y zeolite material, but mineral acid or mineral alkali are handled part silicon source and aluminium source in the kaolin will be dissolved in mineral acid or the mineral alkali, loss silicon source and aluminium source; How the solution that dissolves simultaneously behind the sial is handled, and also will increase the environmental protection cost of whole preparation process.
CN 1533982A adopts the former powder crystalization of kaolin to make the nano level y-type zeolite, its NaY content is the heavy % of 30-85, the primary particle of zeolite is bar-shaped xln, plate crystal body or block xln, wherein the diameter of block xln is 50-500nm, the thickness of plate crystal body is 50-200nm, and the diameter of bar-shaped xln is that 50-200nm, length are 100-600nm; Second particle is by bar-shaped xln or bar-shaped xln and plate crystal body, the common nest formula spheroid that makes up of block xln, and sphere diameter is 1000-3000nm.
The median size of EP 0209332A2 and CN1533982A sintetics all about 3000nm, EP0209332A
2The size of unreceipted synthetic materials primary particle contains a large amount of nano level primary particles in the synthetic materials of CN1533982A.The existence of nano-scale particle can improve the outside surface active sites of catalytic material, but the little long-term hydrothermal stability to material of particle has certain influence.
CN 1736866A adopts ultra-fine Coaseries kaolin to synthesize the oarse-grained nanometer NaY zeolite of pure phase, and what this patent was used is the Coaseries kaolin that refers in particular to, and the synthesis of nano NaY of institute zeolite is described in CN1533982A to some extent.The directed agents proportioning of using in this Patent right requirement 4 is different with conventional directed agents, the charge ratio sodium aluminum ratio and the silica alumina ratio that use in the claim 5 are all higher, problems such as the utilization ratio that will cause feeding intake is low, and mother liquor recycling amount is big, and the degree of crystallinity of actual synthetic product is low.
Summary of the invention
The purpose of this invention is to provide a kind of matrix material that contains the double-pore structure y-type zeolite that is different from prior art.
Matrix material provided by the invention, it is characterized in that this matrix material contains the [amorphous of NaY zeolite and surplus, in matrix material weight, the NaY zeolite accounts for 40%～85%, the secondary structure of this matrix material is similar spheroid, the Y zeolite that this similar spheroid is generated by crystallization and change staggered accumulation of the amorphous intermediate of metakaolin that generates in the brilliant process and form, there are slit and hole, the inner also Youchao road of spheroid, granularity is 3000-25000nm, and the surface-area that the BET method records is 280-800M
2/ g, total pore volume 0.35-0.45ml/g, the middle macropore pore volume of 1.7-300nm is 0.05-0.15ml/g, accounts for the 20-35% of total pore volume.
The present invention also provides the preparation method of above-mentioned matrix material, comprises the steps:
(1) kaolin (comprising halloysite, kaolin, halloysite, Coaseries kaolin) is dewatered 500-890 ℃ of roasting, pulverize, obtain particle diameter and be no less than 50% metakaolin powder less than 2 microns powder;
(2) in the metakaolin powder of (1), add silicon source, directed agents, sodium hydroxide solution and water, make proportioning and be (1-2.5) Na
2O: Al
2O
3: (4-9) SiO
2: (40-100) H
2The reacting material mixture of O, wherein the weight ratio of directed agents and metakaolin is 0.1-1.0;
(3) reacting material mixture with (2) stirs crystallization 50-98 ℃ of temperature programming segmentation speed change, and filtration, washing, drying obtain containing double-pore structure y-type zeolite composite products.
The matrix material that contains the y-type zeolite of double-pore structure provided by the invention, be that the roasting at a certain temperature of the former powder of kaolin is made metakaolin, adopt the metakaolin of single temperature roasting under stirring condition, to carry out the double-pore structure y-type zeolite matrix material of the synthetic second particle of in-situ crystallization greater than 3000nm; This material can be used to prepare all kinds of an acidic catalysts, make catalyzer after active ingredient can be used effectively; Because this material has certain particle characteristics and middle macropore characteristics, makes the reaction that catalyzer helps diffusion control, avoids the generation of secondary reaction.
Description of drawings
Fig. 1 is the X-ray diffractogram of sample.
Fig. 2 is the SEM appearance structure of sample, 2000 times.
Fig. 3 is the SEM appearance structure of sample, 20000 times.
Fig. 4 is the nitrogen adsorption hole distribution curve of sample, and among the figure, ■ is conventional gel method NaY, and zero is porosity Composite material of the present invention.
Fig. 5 is the laser particle size distribution plan of sample.
Embodiment
The matrix material that contains the double-pore structure y-type zeolite provided by the invention, it is characterized in that this matrix material contains the [amorphous of NaY zeolite and surplus, in matrix material weight, the NaY zeolite accounts for 40%～85%, the secondary structure of this matrix material is similar spheroid, the Y zeolite that this similar spheroid is generated by crystallization and change staggered accumulation of the amorphous intermediate of metakaolin that generates in the brilliant process and form, there are slit and hole, the inner also Youchao road of spheroid, granularity is 3000-25000nm, and the surface-area that the BET method records is 280-800M
2/ g, total pore volume 0.35-0.45ml/g, the middle macropore pore volume of 1.7-300nm is 0.05-0.15ml/g, accounts for the 20-35% of total pore volume.
Matrix material provided by the invention, said double-pore structure comprise the micropore of NaY zeolite and by the common middle macropore that makes up between NaY zeolite and the unformed intermediate matrix of metakaolin.
Wherein, crystallization obtains the NaY zeolite under the molecular sieve synthesis condition satisfying by metakaolin or kaolin, and content is between 40%～85%; The unformed intermediate matrix of part metakaolin is the unformed material that metakaolin or kaolin obtain under certain alkalescence, certain temperature, mechanical stirring and certain treatment time condition, and the amorphous intermediate matrix content of metakaolin is the surplus outside the NaY zeolite in the matrix material.
Because alkalescence, temperature, alr mode and the treatment time of handling is different, the distribution of the composition of unformed intermediate, structure and middle macropore all has different; The Y zeolite that generates by crystallization and change also different because of treatment condition of spheroidal size that the staggered accumulation of the unformed intermediate matrix of metakaolin that generates in the brilliant process forms.Matrix material provided by the invention has special structure, and the mesopore and the macropore that contain are more, under mesopore and macropore content condition with higher, still has higher surface area, and the surface-area that the BET method records is 280-800M
2/ g, preferred 400-750M
2/ g; Total pore volume is preferably 0.39-0.45ml/g, and the middle macropore pore volume of 1.7-300nm is 0.05-0.150ml/g, accounts for the 20-35% of total pore volume, preferred 25-35%.
In the matrix material provided by the invention, the silica of said NaY zeolite is preferably 4.0-5.2.
The present invention also provides the preparation method of above-mentioned matrix material, comprises the steps:
(1) kaolin is dewatered 500-890 ℃ of roasting, pulverize, obtain particle diameter and be no less than 50% metakaolin powder less than the powder of 2 μ m;
(2) in the metakaolin powder, add silicon source, directed agents, sodium hydroxide solution and water, make proportioning and be (1-2.5) Na
2O: Al
2O
3: (4-9) SiO
2: (40-100) H
2The reacting material mixture of O, wherein the weight ratio of directed agents and metakaolin is 0.1-1.0;
(3) reacting material mixture is stirred crystallization 50-98 ℃ of temperature programming segmentation speed change, filtration, washing and drying obtain containing double-pore structure y-type zeolite composite products.
In preparation method provided by the invention, the said kaolin of step (1) comprises halloysite, kaolin, halloysite, Coaseries kaolin, preferred halloysite, kaolin, halloysite.Crystalline content should be preferably greater than 85 heavy % greater than 75 heavy % in the kaolin.Preferred 600-890 ℃, more preferably 740-860 ℃ of kaolin roasting dehydration temperaturre, roasting time is 1-10 hour, more preferably 2-4 hour.The metakaolin that kaolin obtains after roasting must be through pulverizing, and obtains particle diameter and be no less than 50% less than the powder of 2 μ m, preferably is no less than 80% metakaolin powder.
In preparation method provided by the invention, the said directed agents of step (2) can be synthetic according to the method for routine, for example according to USP3574538, and USP3639099, USP3671191, USP4166099, the preparation method of EP0435625 is synthetic.The composition of directed agents is generally: (10-17) SiO
2: (0.7-1.3) Al
2O
3: (11-18) Na
2O: (200-350) H
2O.
The said silicon of step (2) source can be the raw material of process water glass or other silicon oxide-containing.The sodium aluminate of using in the directed agents is a sodium metaaluminate, Na in the used sodium hydroxide solution
2The concentration of O is the heavy % of 20-40, the heavy % of preferred 25-35.
In preparation method provided by the invention, step (3) adopts temperature programming segmentation speed change to stir crystallization, said temperature programming speed change stirs crystallization and is meant temperature section segmentation constant temperature 0.1-20 hour between 50-80 ℃, stirring velocity 0-1500 rev/min, temperature section constant temperature between 85-98 ℃ 5-20 hour, stirring velocity 100-1000 rev/min, preferred 400-600 rev/min.Total crystallization time is 10-48 hour, preferred 20-32 hour.Drying temperature is 100-120 ℃.
For making the described catalytic cracking reaction that the double-pore structure y-type zeolite is used for heavy oil that contains, should change na-pretreated zeolite wherein into h-type zeolite through ion-exchange or rare earth ion exchanged is Rare Earth Y (REY) or rare earth hydrogen Y (REHY).
The method for preparing h-type zeolite is the ammonium exchange, and promptly with being selected from ammonium chloride or ammonium nitrate, concentration is that the soluble ammonium salts solution of the heavy % of 4-10 carries out ion-exchange to zeolite, and dry then, a 500-600 ℃ roasting obtains.
The method for preparing REY is that the h-type zeolite that the ammonium exchange once obtains is exchanged with the soluble ree compound solution, the exchange after drying, and 500-600 ℃ of roasting, and then carry out ammonium exchange one to three time, and the earth solution exchange, dry then.The preferred chlorination mishmetal of soluble ree compound also can be the muriate or the nitrate of other rare earth element.Preferred rare earth element is lanthanum, cerium, praseodymium, neodymium, europium or ytterbium, and the character and the rare earth of yttrium are approaching, also can be used to carry out ion-exchange.When using rare earth ion exchanged, the content of zeolite middle-weight rare earths is counted the heavy % of 0.1-21 with oxide compound.The sodium content of zeolite is less than 0.3 heavy %, preferably less than 0.2 heavy % after the rare earth ion exchanged.
Matrix material provided by the invention is applicable to the catalyzed reaction of all kinds of solid acids, and particularly suitable is made the active ingredient of the fluidized catalytic cracking catalyst of heavy oil or residual oil.After rare earth exchanged, have higher hydrothermal stability and anti-carbon deposition ability.Using matrix material provided by the invention and be the suitable condition that catalyzer carries out heavy oil or slag oil cracking is 460-520 ℃, and agent/oil quality is than being 1.0-5.0, when the raw materials quality air speed is 16-45
-1
The invention will be further described below by embodiment, but content not thereby limiting the invention.
Among the embodiment, the relative crystallinity that the NaY content of zeolite is measured according to the RIPP146-90 standard method draws lattice constant a
0Measure according to the RIPP145-90 standard method, the content of REO is measured according to the RIPP131-90 standard method.
The zeolite silica alumina ratio is to measure lattice constant a earlier
0, calculate silica alumina ratio according to following formula again:
SiO
2/ Al
2O
3(mol ratio)=2 * (25.858-a
0)/(a
0-24.191)
The zeolite specific surface area is measured according to nitrogen adsorption method (GB/T5816-1995), and pore volume is measured according to nitrogen adsorption method (RIPP151-90).
Described RIPP measuring method is seen " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, and Science Press, nineteen ninety publishes.
The preparation of directed agents: get the 250 gram sodium silicate solution (SiO that contain 20.05 heavy %
2, 6.41 heavy % Na
2O), 30 ℃ are stirred down the slowly adding 120 gram sodium aluminate solution (Al that contain 3.15 heavy % fast
2O
3, the Na of 21.1 heavy %
2O), stirred 1 hour, 26 ℃ left standstill aging 24 hours, and obtained directed agents.Directed agents consists of 16Na
2O: Al
2O
3: 15 SiO
2: 320H
2O (down together).
With median size is the kaolin (China Kaolin Co., Ltd, crystalline content is 80 heavy % for Suzhou, Yangshan board) of 4 μ m, 800 ℃ of roastings 4 hours, obtains the metakaolin powder, pulverizes to make particle diameter and be no less than 50% metakaolin powder less than the powder of 2.0 μ m.
Get the metakaolin powder after 500 grams are pulverized, stir the 2500 gram sodium silicate solution (SiO that contain 20.05 heavy % of adding down
2, the Na of 6.41 heavy %
2O), 200 gram directed agents, 80 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 1000 grams.Be warming up to 75 ℃ and stirred 10 hours, mixing speed is 1000 rev/mins, and 90 ℃ of constant temperature stirred crystallization 28 hours, and mixing speed is 200 rev/mins.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain Y-1.
The surface-area that the BET method records is 726M
2/ g, total pore volume 0.42ml/g, the middle macropore pore volume of 1.7-300nm is 0.130ml/g, accounts for 32.5% of total pore volume.
The X-diffraction spectrogram (Fig. 1) of Y-1 can find out that zeolite has the characteristic peak of NaY, can extrapolate the content of NaY from the peak area of characteristic peak, and matrix material is made up of the [amorphous of 71%NaY zeolite and 29%, and lattice constant is 2.470nm.
Fig. 2, Fig. 3 is SEM appearance structure figure, be respectively 2000 times and 20000 times, the secondary structure that shows matrix material among the figure is similar spheroid, the Y zeolite that this spheroid is generated by crystallization and change staggered accumulation of the unformed intermediate matrix of metakaolin that generates in the brilliant process and form, have a large amount of slits and hole, the inner also Youchao road of spheroid.
Fig. 4 is pore distribution figure, mesopore and big pore distribution that the curve display matrix material of zero-representative contains at 20-100nm, and the curve of ■-representative concentrates on micropore for the synthetic main duct of NaY zeolite that obtains of conventional gel hydrothermal crystallization method among the figure.
Fig. 5 is the size distribution figure of laser particle size, shows that the granularity of matrix material is median size 15000nm.
Get the metakaolin powder after 500 gram embodiment 1 pulverize, stir the 2500 gram sodium silicate solution (SiO that contain 20.05 heavy % of adding down
2, the Na of 6.41 heavy %
2O), 200 gram directed agents, 120 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 1000 grams.Be warming up to 75 ℃ and stirred 2 hours, mixing speed was 1000 rev/mins, 75 ℃ of static constant temperature 8 hours; Be warming up to 90 ℃ under stirring, constant temperature stirred crystallization 28 hours, and mixing speed is 200 rev/mins.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain matrix material Y-2.
Y-2 has Fig. 2,3 feature, measures through X-ray diffraction, and wherein NaY content is 80.4 heavy %, and lattice constant is 2.472nm, and granularity is median size 5000nm, and the surface-area that the BET method records is 745 meters
2/ gram, total pore volume 0.44ml/g, the middle macropore pore volume of 1.7-300nm is 0.130ml/g, accounts for 29.5% of total pore volume.
Embodiment 3
Get the metakaolin powder after 500 gram embodiment 1 pulverize, 25 ℃ of stirrings add the 2500 gram sodium silicate solution (SiO that contain 20.05 heavy % down
2, the Na of 6.41 heavy %
2O), 200 gram directed agents, 80 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 1000 grams.Be warming up to 50 ℃ and stirred 0.5 hour, 1000 rev/mins of mixing speed are warming up to 95 ℃, crystallization 24 hours, and mixing speed is 500 rev/mins.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain matrix material Y-3.
Y-3 has Fig. 2,3 feature, measures through X-ray diffraction, and wherein NaY content is 60.4 heavy %, and lattice constant is 2.468nm.Granularity is median size 6000nm, and the surface-area that the BET method records is 668M
2/ g, total pore volume 0.40ml/g, the middle macropore pore volume of 1.7-300nm is 0.12ml/g, accounts for 30% of total pore volume.
Get the metakaolin powder after 500 gram embodiment 1 pulverize, stir the 3000 gram sodium silicate solution (SiO that contain 20.05 heavy % of adding down
2, the Na of 6.41 heavy %
2O), 200 gram directed agents, 80 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 1000 grams.Be warming up to 50 ℃ and stirred 10 hours, mixing speed is 1000 rev/mins, and 95 ℃ of constant temperature stirred crystallization 28 hours, and mixing speed is 800 rev/mins.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain matrix material Y-4.
Y-4 has Fig. 2,3 feature, measures through X-ray diffraction, and NaY content is 70.4 heavy %, and lattice constant is 2.468nm.Granularity is median size 12000nm, and the surface-area that the BET method records is 698M
2/ g, total pore volume 0.39ml/g, the middle macropore pore volume of 1.7-300nm is 0.12ml/g, accounts for 30.8% of total pore volume.
Get the metakaolin powder after 500 gram embodiment 1 pulverize, stir the 2500 gram sodium silicate solution (SiO that contain 20.05 heavy % of adding down
2, the Na of 6.41 heavy %
2O), 500 gram directed agents, 80 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 1000 grams.Be warming up to 60 ℃ and stirred 2 hours, mixing speed is 1000 rev/mins, and 95 ℃ of constant temperature stirred crystallization 28 hours, and mixing speed is 400 rev/mins.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain matrix material Y-5.
Y-5 has Fig. 2,3 feature, measures through X-ray diffraction, and NaY content is 55.4 heavy %, and lattice constant is 2.472nm.Granularity is median size 10000nm, and the surface-area that the BET method records is 626M
2/ g, total pore volume 0.35ml/g, the middle macropore pore volume of 1.7-300nm is 0.09ml/g, accounts for 25.7% of total pore volume.
Get 500 grams and pulverize the back particle diameters and be no less than 80% metakaolin powder, stir and add the 2500 gram sodium silicate solutions (SiO that contain 20.05 heavy % down less than the powder of 2 μ m
2, the Na of 6.41 heavy %
2O), 500 gram directed agents, 80 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 2000 grams.Be warming up to 75 ℃ and stirred 10 hours, mixing speed is 1000 rev/mins, and 90 ℃ of constant temperature stirred crystallization 28 hours, and mixing speed is 200 rev/mins.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain matrix material Y-6.
Y-6 has Fig. 2,3 feature, measures through X-ray diffraction, and NaY content is 75.4 heavy %, and lattice constant is 2.470nm.The granularity of material is that the surface-area that median size 7000nm.BET method records is 716M
2/ g, total pore volume 0.41ml/g, the middle macropore pore volume of 1.7-300nm is 0.13ml/g, accounts for 31.7% of total pore volume.
Comparative Examples 1
Kaolinic roasting condition is 990 ℃, and 1h, the roasting condition of metakaolin are 730 ℃, 3h; With water glass 530mL, sodium hydroxide solution 248mL, directed agents 120mL, high soil 56 grams, soil 240 grams drop into reactors partially, 90 ℃ of crystallization 28 hours, get matrix material DB1.
DB1 measures through X-ray diffraction, and wherein NaY content is 62 heavy %, and lattice constant is 2.469nm.The granularity of DB1 is median size 2000nm, and the surface-area that the BET method records is 658 meters
2/ gram, total pore volume 0.32ml/g, the middle macropore pore volume of 1.7-300nm is 0.06ml/g, accounts for 18.8% of total pore volume.
Comparative Examples 2
Inner Mongol Coaseries kaolin gets metakaolin through 800 ℃ of roasting 3h, 11.2 gram sodium hydroxide are added in the 92.2 gram deionized waters, add metakaolin 26.9 grams, add 214.4 gram water glass fully behind the mixing, stirred after 10 minutes the room temperature ageing 24 hours, and added 5% directed agents, stirred 10 minutes under the room temperature, 90 ℃ of crystallization 36 hours, comparative composite DB2.
DB2 measures through X-ray diffraction, and wherein NaY content is 62 heavy %, and lattice constant is 2.468nm.The granularity of DB2 is median size 11000nm, and the surface-area that the BET method records is 592 meters
2/ gram, total pore volume 0.34ml/g, the middle macropore pore volume of 1.7-300nm is 0.06ml/g, accounts for 17.6% of total pore volume
Comparative Examples 3
Get the metakaolin powder after 500 grams are pulverized, stir the 2500 gram sodium silicate solution (SiO that contain 20.05 heavy % of adding down
2, the Na of 6.41 heavy %
2O), the directed agents of 500 gram (1) step preparations, 80 gram concentration are the sodium hydroxide solution of 30 heavy %, deionized water 2000 grams.90 ℃ of static crystallization of constant temperature 28 hours.After crystallization finishes,, filter, be washed to washing lotion pH value less than 10 with the cooling of crystallization jar.120 ℃ of dryings 2 hours obtain comparative composite DB3.
DB3 measures through X-ray diffraction, and wherein NaY content is 72 heavy %, and lattice constant is 2.471nm.The granularity of DB3 is median size 3000nm, and the surface-area that the BET method records is 726M
2/ g, total pore volume 0.35ml/g, the middle macropore pore volume of 1.7-300nm is 0.04ml/g, accounts for 11.4% of total pore volume.
Embodiment 7
Y-3 is adopted the ammonium exchange once, the h-type zeolite that obtains is again with the exchange of soluble ree compound solution, 500-600 ℃ of roasting 2 hours, and then with soluble ree compound solution exchange once, content of rare earth in the rare earth hydrogen Y zeolite of rare earth oxide 17%, get the Y-3 after the modification, add kaolin, pseudo-boehmite, aluminium colloidal sol, their part by weight is 25: 45: 25: 5, and the spray-dried fluidized catalytic cracking catalyst microballoon of making is C-Y-3 test agent.
Method is got same amount DB1 with method of modifying and the method for preparing catalyst of above-mentioned Y-3, obtains the C-DB1 contrast medium.
Adopt small fixed flowing bed to use force and mix two kinds of catalyzer of three oil evaluations, evaluating data is listed in the table 1.
Table 1
| Catalyzer | ??C-Y-3 | ??C-DB1 |
| Stock oil | Military mixed three | Military mixed three |
| Temperature of reaction, ℃ | ??500 | ??500 |
| Agent-oil ratio, wt/wt | ??7.03 | ??7.03 |
| Air speed | ??16 | ??16 |
| Dry gas | ??0.99 | ??1.02 |
| Liquefied gas | ??12.66 | ??12.21 |
| Coke | ??5.1 | ??5.08 |
| Gasoline | ??55.42 | ??52.67 |
| Diesel oil | ??14.93 | ??15.19 |
| Slurry oil | ??10.91 | ??12.93 |
| Transformation efficiency wt% | ??74.16 | ??71.88 |
| Catalyzer | ??C-Y-3 | ??C-DB1 |
| 800 ℃/12h, little work | ??57 | ??58 |
| ??n-P | ??3.4 | ??3.3 |
| ??i-P | ??30.91 | ??29.07 |
| ??O | ??27.5 | ??31.39 |
| ??N | ??9.5 | ??9.25 |
| ??A | ??28.48 | ??26.85 |
| ??RON-GC | ??83.9 | ??84.9 |
| ??MON-GC | ??82.4 | ??83.1 |
Under the situation that data presentation, coke identical in little work etc. worked as in the table 1, the test agent that contains sample of the present invention than the slurry oil of contrast medium lack, transformation efficiency is high, yield of gasoline is high.
Claims (8)
1. matrix material that contains the double-pore structure y-type zeolite, it is characterized in that this matrix material contains the [amorphous of NaY zeolite and surplus, in matrix material weight, the NaY zeolite accounts for 40%～85%, the secondary structure of this matrix material is similar spheroid, the Y zeolite that this similar spheroid is generated by crystallization and change staggered accumulation of the amorphous intermediate of metakaolin that generates in the brilliant process and form, there are slit and hole, the inner also Youchao road of spheroid, granularity is 3000-25000nm, and the surface-area that the BET method records is 280-800M
2/ g, total pore volume 0.35-0.45ml/g, the middle macropore pore volume of 1.7-300nm is 0.05-0.150ml/g, accounts for the 20-35% of total pore volume.
2. according to the matrix material of claim 1, wherein the silica of NaY zeolite is 4.0-5.2.
3. according to the matrix material of claim 1, wherein said total pore volume is 0.39-0.45ml/g.
4. according to the matrix material of claim 1, wherein the middle macropore pore volume of said 1.7-300nm accounts for the 25-35% of total pore volume.
5. the preparation method of the matrix material of claim 1 is characterized in that comprising the steps:
(1) kaolin is dewatered 500-890 ℃ of roasting, pulverize, obtain particle diameter and be no less than 50% metakaolin powder less than the powder of 2 μ m;
(2) in the metakaolin powder, add silicon source, directed agents, sodium hydroxide and water, make mole proportioning and be (1-2.5) Na
2O: Al
2O
3: (4-9) SiO
2: (40-100) H
2The reacting material mixture of O, wherein the weight ratio of directed agents and metakaolin is 0.1-1;
(3) reacting material mixture is stirred crystallization 50-98 ℃ of segmentation, filtration, washing, drying obtain containing the composite products of double-pore structure y-type zeolite.
6. according to the preparation method of claim 5, wherein (1) said kaolin is halloysite, kaolin, halloysite, Coaseries kaolin.
7. according to the preparation method of claim 5, wherein (1) said metakaolin powder footpath is no less than 80% less than the powder of 2 μ m.
8. according to the preparation method of claim 5, wherein in (3) said segmentation to stir crystallization be temperature section segmentation constant temperature 0.1-20 hour between 50-80 ℃, stirring velocity 0-1500 rev/min; Temperature section constant temperature between 85-98 ℃ 5-20 hour, stirring velocity 100-1000 rev/min.
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Cited By (4)
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|---|---|---|---|---|
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN104211084A (en) * | 2014-09-03 | 2014-12-17 | 中国海洋石油总公司 | Preparation method of integrated NaY molecular sieve with high silica-alumina ratio |
| CN112441597A (en) * | 2019-08-30 | 2021-03-05 | 湖南聚力催化剂股份有限公司 | Preparation method of Y-type molecular sieve |
| CN113828350A (en) * | 2020-06-23 | 2021-12-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
Family Cites Families (3)
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| CN1162325C (en) * | 2001-06-29 | 2004-08-18 | 中国石油天然气股份有限公司 | Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition |
| CN1291917C (en) * | 2004-06-16 | 2006-12-27 | 中国石油化工股份有限公司 | Method for synthesizing Y-zeolite composite material |
| CN1307287C (en) * | 2004-08-31 | 2007-03-28 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalyst |
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| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN104211084A (en) * | 2014-09-03 | 2014-12-17 | 中国海洋石油总公司 | Preparation method of integrated NaY molecular sieve with high silica-alumina ratio |
| CN104211084B (en) * | 2014-09-03 | 2016-06-15 | 中国海洋石油总公司 | A kind of preparation method of monoblock type high silica alumina ratio NaY molecular sieve |
| CN112441597A (en) * | 2019-08-30 | 2021-03-05 | 湖南聚力催化剂股份有限公司 | Preparation method of Y-type molecular sieve |
| CN113828350A (en) * | 2020-06-23 | 2021-12-24 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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