CN102949986A - Mesoporous acid silicon-aluminum catalytic material - Google Patents
Mesoporous acid silicon-aluminum catalytic material Download PDFInfo
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Abstract
The invention discloses a mesoporous acid silicon-aluminum catalytic material which is of a pseudo boehmite crystalline phase structure. Based on the oxide weight, the anhydrous chemical expression of the material is (0-0.2)Na2O.(16-20)SiO2.(80-84)Al2O3, the specific surface area is 300-600m<2>/g, the pore volume is 1.0-2.0ml/g, the average pore size is 8-20nm, and the ratio of pyridine infrared B acid to L acid measured at 200 DEG C is 0.060-0.085. The material disclosed by the invention has obvious mesoporous characteristics and centralized pore distribution, and contains the centers of B acid and L acid at the same time; and moreover, the ratio of the B acid to the L acid is obviously increased, and the material obtains better light oil micro-activity.
Description
Technical field
The present invention relates to a kind of acid Si-Al catalysis material, further say a kind of have high B acid ratio, high activity, the obvious acid Si-Al catalysis material of middle hole characteristic.
Background technology
Catalytic cracking and hydrocracking are two very important technical process in the petroleum refining process, are widely used in occupying very important status in the PETROLEUM PROCESSING industry in oil plant.In catalytic cracking and hydrocracking process, heavy end such as vacuum distillate or the residual oil that divides of more recombinating react in the presence of catalyst, be converted into gasoline, distillate and other liquid cracked product and the lighter following gaseous state cracked product of four carbon, in these courses of reaction, usually need to use the catalysis material with peracidity and high cracking activity.
The micro porous molecular sieve material is widely used in petroleum refining and the processing industry owing to having stronger acid and very high catalytic reaction activity.But along with day by day exhausting and variation tendency that crude oil heaviness, in poor quality and intermingled dregs ratio example improve constantly of petroleum resources, particularly market is to the wilderness demand of light-end products, in PETROLEUM PROCESSING, more and more pay attention in recent years the deep processing to heavy oil, residual oil, the part refinery has begun to mix refining decompression residuum, even directly take reduced crude as cracked stock.Traditional micro porous molecular sieve duct is less, and channel diameter is generally less than 2nm, and the restriction in duct is apparent in view, is not suitable for the macromolecular catalytic reactions such as heavy oil or residual oil.
The amorphous silicon aluminum is a kind of acid material equally, not only has the B acid site but also have the L acid site, be the main active component in the early stage catalytic cracking catalyst, but substituted by crystalline molecular sieve gradually owing to the lower and needed reaction temperature of its cracking activity is higher.But in the hydrocracking reaction process, because the aperture of amorphous silicon aluminum is larger, pore-size distribution is wider, and has the acid catalytic property that relatively relaxes, and therefore is widely used as the carrier material in the hydrocracking.
Define according to IUPAC, the aperture is (Jie) hole material in the material of 2～50nm is, and the macromolecular size range such as heavy oil is in this aperture category, thus mesopore material particularly the research of mesoporous silicon aluminum caused catalytic field researcher's very big interest.US5,051,385 discloses a kind of single mesoporous silicon aluminium composite material that disperses, and makes adding alkali reaction after acid inorganic aluminate and the Ludox mixing again, and wherein aluminium content is 5～40 % by weight, aperture 20～50nm, specific area 50～100m
2/ g.US4,708, disclosed in 945 is elder generation's load silicon oxide particle or hydrated silica on the porous boehmite, again with the gained compound at hydrothermal treatment consists certain hour more than 600 ℃, make silica supported at the lip-deep catalyst of class boehmite, wherein silica combines with the hydroxyl of transition state boehmite, and surface area reaches 100～200m
2/ g, average pore size 7～7.5nm.US4 discloses a series of acid Cracking catalyst in 440,872, and the carrier of some of them catalyst is by at γ-Al
2O
3Then upper dipping silane make after 500 ℃ of roastings or steam treatment.US2,394,796 disclose at porous hydrated alumina dipping silicon tetrachloride or silicon tetraethyl, then obtain aluminium silicon composite material through hydrolysis.Adopting inorganic aluminate and waterglass among the CN1353008A is raw material, forms stable clearly silicon-aluminum sol through processes such as precipitation, washing, dispergation, obtains white gels by drying, obtains Si-Al catalysis material in 1～20 hour 350 ℃～650 ℃ lower roastings again.Disclose a kind of mesoporous silicon aluminum in CN1565733A, this silica-alumina material has structure of similar to thin diaspore, and pore-size distribution is concentrated, and specific area is 200～400m approximately
2/ g, pore volume 0.5～2.0ml/g, average pore size is between 8～20nm, and the most probable aperture is 5～15nm.The preparation of this mesoporous silicon aluminum need not used organic formwork agent, and synthetic cost is low, and the silica-alumina material that obtains has high cracking activity and hydrothermal stability, shows good large molecule cracking performance in catalytic cracking reaction.
For the amorphous silicon aluminum, the formation in its acid site mainly is that this bonding structure is the basis that consists of the acid site owing to having formed effective Si-O-Al key.But the Si-O-Al key that forms in conventional amorphous silicon aluminum is fewer, mainly be since silicon source and aluminium to be derived from the aggregation tendency of body larger, the degree of polymerization of primary ion is larger in the aqueous solution, therefore the ratio of silicon, the further bonding formation of aluminium primary ion Si-O-Al key is very low, and the acidity of the silica-alumina material that obtains is lower.US4, disclose in 226,743 a kind of by silicate, acidity or basic aluminium salt such as aluminum sulfate or sodium metaaluminate be raw material by the method for the standby silica-alumina material of common glue legal system, reach the purpose of improving sial bonding state by alkalescence to the modulation of acidity by pH value.US4,003,825 discloses and a kind ofly has been hydrolyzed the method for preparing silica-alumina material by organo-silicon compound in the aqueous solution of aluminum nitrate, but the organosilicon price is more expensive and stable some problems arranged.US5,045,519 discloses a kind of method that aluminum alkoxide and positive silicic acid mixed hydrolysis is prepared silica-alumina material in aqueous medium, the material that this method obtains has structure of similar to thin diaspore, and impurity content is low, Heat stability is good, acidity is stronger, but the distribution between the sial is not too even.In order to improve the uniformity of silica-alumina material, US6,872, in 685 silicate solutions and acid aluminium salt solution are mixed under intense agitation, form the Ludox under the existence of aluminium salt, and then mix with alkaline precipitating agent and to form altogether colloidal sol, thereby prepare the amorphous silicon aluminum of high uniformity.It adopts the mutually ratio of sial atomic ratio-be the SB value of surface and body, characterize the uniformity of amorphous silicon aluminum, and compare with MS-25 (Grace company) with two kinds of commercial silica-alumina material Siral 40 (Sasol company), the SB value all will be more near 1, the uniformity that the amorphous aluminum silicide that this legal system is standby is described is stronger, and acidity is also higher.
Summary of the invention
The purpose of this invention is to provide a kind of high B acid ratio, high activity, the obvious acid Si-Al catalysis material of middle pore property.
Acid Si-Al catalysis material provided by the invention has the boehmite crystal phase structure, and in oxide weight, its anhydrous chemical expression is: (0～0.2) Na
2O (16～20) SiO
2(80～84) Al
2O
3, its specific area is 300～600m
2/ g, preferred 400～550m
2/ g, pore volume are 1.0～2.0ml/g, preferred 1.2～1.7ml/g, and average pore size is 8～20nm, and preferred 10～15nm is characterized in that, and the infrared B acid of the pyridine that this catalysis material records under 200 ℃ of conditions is 0.060～0.085 with the ratio of L acid.
The infrared B acid that records of said pyridine is to adopt pyridine temperature programming infra-red sepectrometry to obtain with L acid.With sample self-supporting compressing tablet, place the original position pond of infrared spectrometer to seal, be warming up to 350 ℃ and be evacuated to 10-3Pa, constant temperature removes the gas molecule of sample absorption after 1 hour; Be cooled to and import the pyridine steam after the room temperature and kept adsorption equilibrium 30 minutes, then be warming up to 200 ℃, again be evacuated to 10-3Pa and under this vacuum desorption 30 minutes, be down to room temperature and take the photograph spectrum, sweep limits 1400～1700cm
-1, can obtain sample through the pyridine adsorption infrared spectrogram of 200 ℃ of desorptions.According to 1540cm in the pyridine adsorption infrared spectrogram
-1And 1450cm
-1The intensity of characteristic absorption peak is calculated the relative quantity in B acid site and L acid site.
The acid Si-Al catalysis material of the said mesopore of the present invention is to prepare with the process that comprises the steps, the method is:
(1) aluminium source and aqueous slkali are neutralized into glue under room temperature to 85 ℃, becoming glue terminal point pH is 7～11;
(2) according to SiO
2: Al
2O
3=1: the weight ratio of (4～6) added the silicon source, room temperature to 90 ℃ lower ripening 1～10 hour;
(3) the gained solid sediment is carried out ammonium exchange or foreign ion is removed in the acid exchange;
(4) with behind the filter cake reslurry according to fluosilicic acid: material butt=(0.01～0.12): 1 weight ratio and fluosilicic acid contact under room temperature to 80 ℃ and mixed at least 0.5 hour;
(5) after the filtration washing, lower dry 10～20 hours at 100 ℃～150 ℃.
In the said preparation process, the aluminium source of step (1) is selected from one or more in aluminum nitrate, aluminum sulfate or the aluminium chloride; Said alkali is selected from one or more in ammoniacal liquor, potassium hydroxide, NaOH and the sodium metaaluminate; The silicon source of step (2) is selected from one or more in waterglass, sodium metasilicate, silicon tetraethyl and the silica.
In the said preparation process, the process of the said ammonium of step (3) exchange is well known to those skilled in the art, and the solid sediment that normally will obtain through step (2) ripening is by sediment (butt): ammonium salt: H
2O=1: (0.1～1): the weight ratio of (10～30) exchanges 0.5～1 hour, until sodium content is lower than 0.2% in the solid sediment room temperature to 100 ℃ lower exchange 1～3 time at every turn.In the said ammonium exchange process, ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and the carbonic hydroammonium.
In the said preparation process, the process of the said acid exchange of step (3) is the solid sediment that will obtain through step (2) ripening by sediment (butt): acid: H
2O=1: (0.03～0.30): the weight ratio of (5～30) exchanges 0.2 hour at least under room temperature to 100 ℃.The acid of using in the said acid exchange is generally inorganic acid, can be selected from sulfuric acid, hydrochloric acid or nitric acid.
In the said preparation process, the hybrid mode of the said fluosilicic acid of step (4) and material slurries can have multiple, for example be that fluosilicic acid is added drop-wise in the material slurries, also the material slurries can be joined in the fluorine silicic acid aqueous solution of dilution, wherein, preferably fluosilicic acid is added drop-wise to mode in the material slurries.
In the said preparation process, the said recovery of step (5) is well known to those skilled in the art, and this numerous stating no longer, typically refers to after product is filtered washing, 100 ℃～150 ℃ lower dry processes.
Pore property is obvious in the acid Si-Al catalysis material provided by the present invention, and pore distribution concentration contains B acid and L acid site simultaneously, and B is sour and L acid ratio obviously improves, and material has better light oil microactivity.In addition, acid Si-Al catalysis material provided by the present invention has higher degree of crystallinity.
Description of drawings
Accompanying drawing is the X-ray diffraction spectrogram of the acid Si-Al catalysis material of mesopore.
The specific embodiment
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In each embodiment, the Na of sample
2O, Al
2O
3, SiO
2Content is measured (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication) with x-ray fluorescence method.
The phase of sample and crystallinity data adopt X-ray diffraction method to measure.
The materialization the data nitrogen absorption under low temperatures such as the specific surface of sample, pore structure-desorption method is measured.
The infrared pyridine adsorption in site measurement of the acid the data method of sample is measured.
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
The preparation process of the present embodiment is with the process described in the CN1565733A.Getting an amount of concentration is 90gAl
2O
3The Al of/L
2(SO
4)
3Solution places beaker, under stirring condition ammoniacal liquor is dropwise added, until system pH=9, being neutralized into the glue temperature is 50 ℃; The concentration that adds metering under stirring condition is 60gSiO
2The waterglass of/L is warming up to 80 ℃ of ageings 4 hours; Use NH
4Cl solution is pressed sediment (butt): ammonium salt: H
2O=1: 0.5: 10 weight ratio, under 60 ℃, the sial sediment to be carried out ion-exchange and remove sodium ion, exchange repeats twice, carries out 0.5 hour at every turn, then gained filter cake reslurry is also pressed fluosilicic acid: material butt: H
2O=0.03: 1: 10 weight ratio is added drop-wise to required fluosilicic acid in the slurries of material, 50 ℃ of lower stirring reactions 1.5 hours, filters after the washing in 120 ℃ and namely gets acid Si-Al catalysis material provided by the invention in lower dry 15 hours, is designated as BSA-1.
The X-ray diffraction spectral line of BSA-1 is shown among Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in table 1; The hole parameters such as specific area and infrared acid data rows are in table 2.
Comparative Examples 1
Getting an amount of concentration is 90gAl
2O
3The Al of/L
2(SO
4)
3Solution places beaker, under stirring condition ammoniacal liquor is dropwise added, until system pH=9, being neutralized into the glue temperature is 50 ℃; The concentration that adds metering under stirring condition is 60gSiO
2The waterglass of/L is warming up to 80 ℃ of ageings 4 hours; Use NH
4Cl solution is pressed sediment (butt): ammonium salt: H
2O=1: 0.5: 10 weight ratio, under 60 ℃, the sial sediment to be carried out ion-exchange and remove sodium ion, exchange repeats twice, carries out 0.5 hour at every turn, namely gets the Si-Al catalysis materials of contrast in 15 hours in 120 ℃ of lower dryings after filtering.Be designated as DB-1.
The X-ray diffraction spectral line of comparative sample DB-1 is shown in Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in table 1; The hole parameters such as specific area and infrared acid data rows are in table 2.
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
Preparation process is with embodiment 1, and wherein the additional proportion of fluosilicic acid is fluosilicic acid: material butt: H
2O=0.06: 1: 10, namely get acid Si-Al catalysis material after the washing oven dry.Be designated as BSA-2.
The X-ray diffraction spectral line of BSA-2 is shown in Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in table 1; The hole parameters such as specific area and infrared acid data rows are in table 2.
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
Preparation process is with embodiment 1, and wherein the additional proportion of fluosilicic acid is fluosilicic acid: material butt: H
20=0.09: 1: 10, namely get acid Si-Al catalysis material after the washing oven dry.Be designated as BSA-3.
The X-ray diffraction spectral line of BSA-3 is shown in Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in table 1; The hole parameters such as specific area and infrared acid data rows are in table 2.
Table 1
| The sample title | Degree of crystallinity/% | Na 2O/％ | Al 2O 3/％ | SiO 2/％ |
| BSA-1 | 54.5 | 0.09 | 82.3 | 17.1 |
| BSA-2 | 56.0 | 0.11 | 82.4 | 17.0 |
| BSA-3 | 57.4 | 0.10 | 81.9 | 17.4 |
| DB-1 | 50.6 | 0.11 | 81.7 | 17.5 |
Table 2
By table as seen, it is higher that the acid Si-Al catalysis material of mesopore provided by the invention and contrast material DB-1 compare degree of crystallinity, and B acid significantly improves with the ratio of L acid, compares to exceed more than one times than material DB-1.
Embodiment 4
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
The preparation process of the present embodiment is with the process described in the CN1565733A.Take concentration as 90gAl
2O
3The Al of/L
2(SO
4)
3Solution and concentration are 102gAl
2O
3/ L, causticity are than 2.5 NaAlO
2Solution is reaction raw materials, and stream becomes glue and be adjusted to glue pH=10.5, collects a certain amount of one-tenth rubber cement liquid, and adding quantitative concentrations under stirring condition is 60gSiO
2The waterglass of/L is warming up to 70 ℃ of ageings 2 hours; Press sediment (butt) with NH4Cl solution: ammonium salt: H
2O=1: 1: 15 weight ratio, under 60 ℃, the sial sediment to be carried out ion-exchange and remove sodium ion, exchange repeats twice, carries out 0.5 hour at every turn, then gained filter cake reslurry is also pressed fluosilicic acid: material butt: H
2O=0.02: 1: 8 weight ratio is added drop-wise to required fluosilicic acid in the slurries of material, 70 ℃ of lower reactions 1 hour, namely gets acid Si-Al catalysis material provided by the invention in 15 hours in 120 ℃ of lower dryings after the filtration washing.Be designated as BSA-4.
The X-ray diffraction spectrogram of BSA-4 is similar to Fig. 1, and figure slightly; Degree of crystallinity and elementary analytical chemistry form lists in the table 3; The hole parameters such as specific area and infrared acid data rows are in table 4.
Embodiment 5
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
Preparation process is with embodiment 4, and wherein the additional proportion of fluosilicic acid is fluosilicic acid: material butt: H
2O=0.10: 1: 8, required fluosilicic acid is added drop-wise in the slurries of material after 30 ℃ of lower reactions 2 hours, namely get acid Si-Al catalysis material after the washing oven dry.Be designated as BSA-5.
X-ray diffraction spectrogram and Fig. 1 of BSA-5 have identical feature; Degree of crystallinity and elementary analytical chemistry form lists in table 3; The hole parameters such as specific area and infrared acid data rows are in table 4.
Embodiment 6
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
Preparation process is wherein pressed fluosilicic acid with embodiment 4: material butt: H
2O=0.05: 1: 12 ratio joins the filter cake slurries in the fluosilicic acid weak solution under vigorous stirring, and 60 ℃ of lower reactions 1 hour, namely gets acid Si-Al catalysis material after the washing oven dry.Be designated as BSA-6.
X-ray diffraction spectrogram and Fig. 1 of BSA-6 have identical feature; Degree of crystallinity and elementary analytical chemistry form lists in table 3; The hole parameters such as specific area and infrared acid data rows are in table 4.
Embodiment 7
This example illustrates the preparation of the acid Si-Al catalysis material of mesopore provided by the invention.
Preparation process is wherein carried out the exchange of solid sediment with embodiment 4 with hydrochloric acid, press sediment (butt): hydrochloric acid: H
2O=1: then 0.14: 10 weight ratio presses fluosilicic acid: material butt: H 70 ℃ of lower exchanges 0.5 hour
2O=0.08: 1: 12 ratio joins the filter cake slurries in the fluosilicic acid weak solution under vigorous stirring, and 60 ℃ of lower reactions 1 hour, namely gets acid Si-Al catalysis material after the washing oven dry.Be designated as BSA-7.
X-ray diffraction spectrogram and Fig. 1 of BSA-7 have identical feature; Degree of crystallinity and elementary analytical chemistry form lists in table 3; The hole parameters such as specific area and infrared acid data rows are in table 4.
Table 3
| The sample title | Degree of crystallinity/% | Na 2O/％ | Al 2O 3/％ | SiO 2/％ |
| BSA-4 | 54.8 | 0.11 | 83.0 | 16.6 |
| BSA-5 | 56.2 | 0.06 | 81.5 | 18.1 |
| BSA-6 | 55.9 | 0.10 | 80.1 | 19.2 |
| BSA-7 | 57.0 | 0.09 | 81.7 | 17.8 |
Table 4
Embodiment 8
This example illustrates the initial cracking activity of the acid Si-Al catalysis material of mesopore provided by the invention.
Then the sample that the sample that above-mentioned example 1～7 is obtained and Comparative Examples 1 obtain is estimated at fixed-bed micro-devices 500 ℃ of lower roastings 1 hour, is initial activity with the little Index Definition alive of the light oil that obtains.Raw materials used oil is the huge port straight distillation light diesel oil of 221 ℃～335 ℃ of boiling ranges, and appreciation condition is oil ratio 1.28, mass space velocity 40.11h
-1, 460 ℃ of reaction temperatures.
Evaluation result is listed in table 5.
Table 5
| The sample title | Initial activity (% by weight) | The sample title | Initial activity (% by weight) |
| DB-1 | 28 | BSA-4 | 32 |
| BSA-1 | 30 | BSA-5 | 34 |
| BSA-2 | 33 | BSA-6 | 35 |
| BSA-3 | 35 | BSA-7 | 31 |
As can be seen from Table 5, the acid Si-Al catalysis material of mesopore provided by the invention has a higher initial activity in the situation that silica alumina ratio is suitable.
Claims (8)
1. the acid Si-Al catalysis material of mesopore has the boehmite crystal phase structure, and in oxide weight, its anhydrous chemical expression is: (0～0.2) Na
2O (16～20) SiO
2(80～84) Al
2O
3, its specific area is 300～600m
2/ g, pore volume are 1.0～2.0ml/g, and average pore size is 8～20nm, it is characterized in that the sour ratio with L acid of the infrared B of pyridine that this catalysis material records under 200 ℃ of conditions is 0.060～0.085.
2. according to the catalysis material of claim 1, wherein, specific area is 400～550m
2/ g, pore volume are 1.2～1.7ml/g, and average pore size is 10～15nm.
3. according to the catalysis material of claim 1, it is characterized in that this material obtains through following steps: (1) is neutralized into glue with aluminium source and aqueous slkali under room temperature to 85 ℃, becoming glue terminal point pH is 7～11; (2) according to SiO
2: Al
2O
3=1: the weight ratio of (4～6) added the silicon source, room temperature to 90 ℃ lower ageing 1～10 hour; (3) the gained solid sediment is carried out ammonium exchange or foreign ion is removed in the acid exchange; (4) with behind the filter cake reslurry according to fluosilicic acid: material butt=(0.01～0.12): 1 weight ratio and fluosilicic acid room temperature to 80 ℃ lower mix contact at least 0.5 hour after recovery.
4. according to the catalysis material of claim 3, wherein, the aluminium source of step (1) is selected from one or more in aluminum nitrate, aluminum sulfate or the aluminium chloride; Said alkali is selected from one or more in ammoniacal liquor, potassium hydroxide, NaOH and the sodium metaaluminate.
5. according to the catalysis material of claim 3, wherein, the silicon source of step (2) is selected from one or more in waterglass, sodium metasilicate, silicon tetraethyl and the silica.
6. according to the catalysis material of claim 3, wherein, the process of the said ammonium exchange of step (3) is the solid sediment that will obtain through step (2) ripening by the sediment butt: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (10～30) is room temperature to 100 ℃ lower exchange 1～3 time, each exchange 0.5～1 hour, until sodium content is lower than 0.2% in the solid sediment, in the said ammonium exchange process, ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and the carbonic hydroammonium.
7. according to the catalysis material of claim 3, wherein, the process of the said acid exchange of step (3) is the solid sediment that will obtain through step (2) ripening by the sediment butt: acid: H
2O=1: (0.03～0.30): the weight ratio of (5～30) exchanges 0.2 hour at least under room temperature to 100 ℃, and the acid of using in the said acid exchange is selected from sulfuric acid, hydrochloric acid or nitric acid.
8. according to the catalysis material of claim 3, wherein, the hybrid mode of the said fluosilicic acid of step (4) and material slurries is for being added drop-wise to fluosilicic acid the mode in the material slurries.
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| CN106807352A (en) * | 2015-12-01 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of active mesoporous Si-Al catalysis material |
| CN106807353A (en) * | 2015-12-01 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of preparation method of active catalytic material |
| CN106809853A (en) * | 2015-11-30 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of active porous catalysis material and preparation method thereof |
| CN108499554A (en) * | 2017-02-24 | 2018-09-07 | 中国石油化工股份有限公司 | A kind of silica-alumina material, preparation method and applications |
| CN108745409A (en) * | 2018-06-05 | 2018-11-06 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for improving gasoline yield and preparation method thereof |
| CN108927123A (en) * | 2017-05-26 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of porous catalyst material and preparation method thereof |
| CN108927128A (en) * | 2017-05-26 | 2018-12-04 | 中国石油化工股份有限公司 | A kind of amorphous catalytic material and preparation method thereof in the high acid site B |
| CN109305689A (en) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | Medium-large pore silicon-aluminum material and preparation method thereof |
| CN113813947A (en) * | 2020-06-19 | 2021-12-21 | 中国石油天然气股份有限公司 | Silicon-aluminum material and preparation method thereof |
| CN114506867A (en) * | 2020-10-29 | 2022-05-17 | 中国石油化工股份有限公司 | Silicon-containing pseudo-boehmite as well as preparation method and application thereof |
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