CN104549383B - A kind of mesoporous active materials and its application with structure of similar to thin diaspore - Google Patents
A kind of mesoporous active materials and its application with structure of similar to thin diaspore Download PDFInfo
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Abstract
A kind of mesoporous active materials of boehmite crystal phase structure, it is characterised in that its anhydrous compound composition is calculated as with oxide weight ratio（0‑0.2）Na2O·（50‑86）Al2O3·（12‑50）SiO2·（0.5‑10）P2O5, the material specific surface area is 200~600m2/ g, pore volume is 0.5~1.8cm3/ g, average pore size is 8~18nm.The preparation of the mesoporous active materials is without the use of organic formwork agent, and synthesis cost is low, and obtained material has high cracking activity and hydrothermal stability, and good macromolecular cracking performance is shown in catalytic cracking reaction.
Description
Technical field
It is in particular to a kind of that there is boehmite knot the present invention relates to a kind of mesoporous active materials and its application
The mesoporous active materials of structure and its application.
Background technology
Catalytic cracking is widely used in PETROLEUM PROCESSING industry as a kind of oil refining process, adds as crude oil is secondary
Mostly important process in work, the technique is the main means of production of liquefied petroleum gas, gasoline, kerosene and diesel oil, in refining
Occupy very important status in oily factory.In catalytic cracking and hydrocracking process, heavy end such as vacuum distillate or more
The residual oil of heavy constituent reacts in the presence of a catalyst, be converted into gasoline, distillate and other liquid cracking products and compared with
Gaseous cracked product below four light carbon, is usually required using the catalysis material with high cracking activity in these courses of reaction
Material.
Micro-pore zeolite catalysis material has excellent shape selective catalysis performance and very high cracking reaction activity due to it, wide
It is applied to generally in petroleum refining and processing industry.With wanting in terms of the increasingly exhaustion of petroleum resources and environmental protection
Ask, particularly crude oil becomes the growth trend of weight increasingly（>500 DEG C of high boiling component increase）With market to a large amount of of light-end products
Demand, increasingly payes attention to the deep processing to heavy oil and residual oil in PETROLEUM PROCESSING industry, and part refinery starts to mix refining decompression slag
Oil, or even directly using reduced crude as cracked stock.Traditional micro porous molecular sieve catalysis material is smaller due to its duct, to larger
Raw molecule show obvious limitation diffusion, cause apparent reaction activity reduction, greatly limit big
The catalytic reaction of molecule, therefore it is not suitable for being applied to the catalytic cracking reaction of the heavy ends such as heavy oil and residual oil.
To improve the heavy oil selectivity of catalytic cracking, it is necessary to convert the macromolecular of heavy oil fraction, while also to subtract
The further conversion of few intermediate oil and naphtha, this is accomplished by using aperture larger, and limit is not spread to reactant molecule
System, and the material with compared with high cracking activity.And traditional micro porous molecular sieve is only beneficial to the cracking of small molecule, thus it is mesoporous and big
The research and development of hole catalysis material are increasingly valued by people.
The appearance of mesopore molecular sieve is, in 1992, to be succeeded in developing first by Mobil companies of the U.S.（Beck J S,
Vartuli J Z, Roth W J et al., J.Am.Chem.Comm.Soc., 1992,114,10834-10843）, it is named as
M41S series mesopore molecular sieves, including MCM-41（Mobil Corporation Material-41）With MCM-48 etc., molecular sieve
Aperture up to 1.6~10nm, uniform adjustable, pore-size distribution is concentrated, and specific surface area and pore volume are big, high adsorption capacity；But by
In the hole wall structure of the molecular sieve analog be undefined structure, therefore hydrothermal stability difference and acid weaker, it is impossible to meet catalysis and split
The operating condition of change, commercial Application is very restricted.
To solve the problem of mesopore molecular sieve hydrothermal stability is poor, part research work concentrates on raising molecular sieve pores wall thickness
Degree, such as can obtain the thicker molecular sieve of hole wall using neutral template, but acid weaker shortcoming is still present.
A kind of new mesopore molecular sieve is disclosed in CN1349929A, the primary and secondary structure of zeolite is introduced in molecular sieve hole wall
Unit, makes it have the basic structure of traditional zeolite molecular sieve, and the mesopore molecular sieve has highly acid and the hydrothermally stable of superelevation
Property.But the deficiency of this molecular sieve is that expensive template need to be used, and aperture only has 2.7nm or so, for big point
Sub- cracking reaction still has structure under larger space steric effect, high temperature hydrothermal condition easily to collapse, and cracking activity is poor.
In catalytic cracking field, silica-alumina material is because it has stronger acid centre and good cracking performance and obtains
To be widely applied.The proposition of mesoporous concept, the again preparation for new catalyst provides possibility, collects current result of study more
In using expensive organic formwork agent and organic silicon source, and majority will pass through high-temperature water heat treatment process.US5051385
In disclose a kind of monodisperse mesoporous aluminium silicon composite material, add alkali after first being mixed acid mineral aluminium salt and Ludox,
The aluminium content of silica-alumina material is obtained in 5~40 heavy %, aperture reaches 50~100m between 20~50nm, specific surface area2/g。
Method disclosed in US4708945 is that silicon oxide particle or hydrated silica are loaded on porous boehmite, then by gained
The silica supported catalyst on class boehmite surface, this material is made in more than 600 DEG C hydro-thermal process in compound
Surface area be 100~200m2/ g, 7~7.5nm of average pore size.Serial sour Cracking catalyst is disclosed in US4440872,
The carrier of some of catalyst is by γ-Al2O3Upper dipping silane, then makes after 500 DEG C of roastings or steam treatment
.US2394796 is disclosed impregnates silicon tetrachloride or silicon tetraethyl on porous hydrated alumina, then obtains sial through hydrolysis
Composite.Inorganic aluminate and waterglass are used in CN1353008 for raw material, forms stable clear by processes such as precipitation, dispergation
Clear silicon-aluminum sol, by white gels are dried to obtain, sial is obtained after being calcined 1~20 hour under the conditions of 350 DEG C~650 DEG C
Catalysis material.US6858555 discloses a kind of catalyst for cracking heavy oil containing mixed-metal oxides such as sieve and silica-sesquioxide, its
Middle sieve and silica-sesquioxide is undefined structure.One kind is disclosed in CN1138566 and is dispersed with silicon, boron, phosphorous oxides, VIII and VIB
The mesoporous alumina gel of family metal oxide, its mainly use organic silicon source, silicon source, boron source and soluble sources for raw material simultaneously
It is dissolved in organic alcoholic solution, adds organic formwork agent and be hydrolyzed and gelation, gained mesoporous gel can be carried as catalyst
Body, acid catalyst or hydrogenation catalyst are used.
A kind of mesoporous silica-alumina materials are disclosed in CN1565733A, the silica-alumina material has boehmite crystalline phase knot
Structure, pore-size distribution is concentrated, specific surface area about 200~400m2/ g, 0.5~2.0ml/g of pore volume, average pore size between 8~20nm,
Most probable pore size is 5~15nm.The preparation of the mesoporous silica-alumina materials is without the use of organic formwork agent, and synthesis cost is low, obtains
Silica-alumina material has high cracking activity and hydrothermal stability, good macromolecular is shown in catalytic cracking reaction cracking
Energy.
The content of the invention
The purpose of the present invention is to provide a kind of mesopore activity with structure of similar to thin diaspore on the basis of existing technology
Material, the material has highly efficient heavy oil conversion performance when being used in catalytic cracking process.
The present inventor has found on the basis of lot of experiments, using the preparation method different from prior art, obtains
To its basic structural unit of material and combination facilitate the change of material composition, resulting active mesopore material has
There is special matching relationship between structure of similar to thin diaspore, each component, phosphorus content has one specific under certain sial ratio
Optimum range, when it is applied in catalyst for heavy oil catalytic cracking or auxiliary agent, show more excellent residual oil cracking performance.
Based on this, the present invention is formed.
A kind of mesoporous active materials for boehmite crystal phase structure that the present invention is provided, it is characterised in that its anhydrous chemical combination
Thing composition is calculated as with oxide weight ratio（0-0.2）Na2O·（50-86）Al2O3·（12-50）SiO2·（0.5-10）P2O5, should
Material specific surface area is 200~600m2/ g, pore volume is 0.5~1.8cm3/ g, average pore size is 8~18nm.It is preferred that, compare surface
Product is 250~550m2/ g, pore volume is 0.6~1.6cm3/ g, average pore size is 9~15nm.
Further, mesoporous active materials of the present invention, it is preferred in terms of oxide weight ratio that its anhydrous compound is constituted
For（0-0.2）Na2O·（50-62）Al2O3·（38-50）SiO2·（0.5-5）P2O5, the preferred specific surface area of the material is
200~400m2/ g, further preferred 250~350m2/g；Preferred pore volume is 0.5~1.2cm3/ g, further preferred 0.6
~1.0cm3/g；Preferred average pore size is 8~15nm, further preferred 9~12nm.
The mesoporous active materials with structure of similar to thin diaspore described in the present invention, are with the process system comprised the steps
Standby to obtain, this method is that control plastic pH value be 7~11 to plastic is neutralized at 85 DEG C by silicon source and aqueous slkali in room temperature；Press
According to SiO2：Al2O3=1：（1~7.5）Weight than adding silicon source, be aged 1~5 hour at 90 DEG C in room temperature；By gained solid
Sediment contacts processing certain time with ammonium salt or acid solution, is filtrated to get the solid sediment that sodium content is less than 0.3%；Will
The solid sediment arrived is with phosphorus source according to P2O5：Material butt=（0.005~0.1）：1 weight is handled than contact, and in 100 DEG C
Dry 10~20 hours, or be calcined 1~4 hour at 500 DEG C~700 DEG C at~150 DEG C.
It is according to SiO in its preparation process for the preferred situation of mesopore material of the present invention2：Al2O3=1：（1~
1.7）Weight than adding silicon source, and by obtained solid sediment and phosphorus source according to P2O5：Material butt=（0.005~
0.05）：1 weight is handled than contact.
In described preparation process, used silicon source is included in the inorganic silicon sources such as aluminum nitrate, aluminum sulfate or aluminium chloride
It is any；Used alkali includes any of ammoniacal liquor, potassium hydroxide, sodium hydroxide or sodium metaaluminate；Used silicon source
Including waterglass, sodium metasilicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon or silica.
In described preparation process, the described process that processing is contacted with ammonium salt is well known to those skilled in the art, led to
It is often the solid sediment by gained by sediment（Butt）：Ammonium salt：H2O=1：（0.1~1）：（5~30）Weight ratio in room
Temperature is exchanged 0.5~1 hour every time to exchange at 100 DEG C 1~3 time, until sodium content is less than 0.3% in solid sediment.It is described
During ammonium salt contact processing, ammonium salt includes one kind or many in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate
Kind.
In described preparation process, the described process that processing is contacted with acid solution, is by step（2）The solid of gained sinks
Starch presses sediment（Butt）：Acid：H2O=1：（0.03~0.3）：（5~30）Weight ratio in room temperature at least handing at 100 DEG C
Change 0.2 hour.The acid used during described acid solution contact processing usually inorganic acid, can selected from sulfuric acid, hydrochloric acid or
Nitric acid.
In described preparation process, the described processing procedure that contacted with phosphorus source can have a variety of, including gained solid is sunk
Starch presses sediment（Butt）：H2O=1：（5~20）Weight ratio mashing is mixed with water, then phosphorus source is added in above-mentioned slurries,
In room temperature to contact processing 0.2~5 hour at 90 DEG C, preferably 0.5~3 hour, done after filtering washing at 100 DEG C~150 DEG C
Dry 10~20 hours；Or directly mix solid sediment in proportion with phosphorus source, after grinding is uniform at 100 DEG C~150 DEG C
Dry 10~20 hours.Dried sample can not be calcined or is calcined 1~4 hour at 500 DEG C~700 DEG C.Used phosphorus
Source can be any of ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphoric acid.
Hole characteristic is obvious in mesoporous active materials provided by the present invention with structure of similar to thin diaspore, residual oil cracking energy
Power is stronger, and coke selectivity more preferably, can apply in RFCC, is used as the active component or work of catalyst or auxiliary agent
Property host material.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of the mesoporous active materials of the structure of similar to thin diaspore of embodiment 1.
Fig. 2 is the X-ray diffraction spectrogram of the material of comparative example 2.
Embodiment
The following examples illustrate the present invention further, but content not thereby limiting the invention.
In embodiments, Na in sample2O、Al2O3、SiO2、P2O5Content determined with x-ray fluorescence method（Referring to《Stone
Oily chemical analysis method（RIPP experimental methods）》, Yang Cui surely compile by grade, and Science Press, nineteen ninety publishes）.Sample thing mutually uses X
Ray diffraction method is determined.Sample specific surface area, pore volume, average pore size are determined by nitrogen absorption under low temperature-desorption method.
Embodiment 1
This example illustrates the preparation for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
With concentration 90gAl2O3/ L Al2(SO4)3Solution and concentration 102gAl2O3/ L, Crater corrosion 1.7 NaAlO2Solution is
Reaction raw materials, cocurrent plastic simultaneously adjusts plastic pH=9.0, collects quantitative plastic slurries, and stirring is lower to add concentration 60gSiO2/ L's
Waterglass, is warming up to 80 DEG C and is aged 1.5 hours；Use NH4Cl solution presses sediment（Butt）：Ammonium salt：H2O=1:1:12 weight
Than at 60 DEG C carrying out ion exchange to sial sediment removes sodium ion, and is eluted to sodium oxide molybdena and contain with a large amount of deionized waters
Amount is less than 0.3%；Then the solid sediment directly by sodium oxide content less than 0.3% presses P with phosphoric acid2O5：Material butt=
0.008：1 weight is than mixing, and uniform dried after 120 DEG C of grinding produces the mesoporous active materials that the present invention is provided for 10 hours.
It is designated as PAM-1.
PAM-1 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is as shown in Figure 1；Its elementary analysis
Chemical composition is 0.14Na2O·59.3Al2O3·39.1SiO2·0.8P2O5；Specific surface area 320m2/ g, pore volume 0.78cm3/ g,
Average pore size 9.7nm.
Embodiment 2
This example illustrates the preparation for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
Preparation process be the same as Example 1.Solid sediment i.e. directly by sodium oxide content less than 0.3% presses P with phosphoric acid2O5：
Material butt=0.02：1 weight is than mixing, and grinding is uniform to be dried 10 hours after 120 DEG C, is calcined 2 hours at 550 DEG C
Produce the mesoporous active materials that the present invention is provided.It is designated as PAM-2.
PAM-2 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with Fig. 1 features；Its elementary analysis
Chemical composition is 0.13Na2O·53.6Al2O3·43.7SiO2·2.0P2O5；Specific surface area 307m2/ g, pore volume 0.91cm3/ g,
Average pore size 11.8nm.
Embodiment 3
This example illustrates the preparation for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
Preparation process be the same as Example 1.Wherein phosphorus source selects ammonium dihydrogen phosphate, the consolidating less than 0.3% directly by sodium oxide content
Body sediment presses P with ammonium dihydrogen phosphate2O5：Material butt=0.04：1 weight is than mixing, and grinding is uniform after 120 DEG C of dryings
10 hours, roasting produced the mesoporous active materials that the present invention is provided for 2 hours at 600 DEG C.It is designated as PAM-3.
PAM-3 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with Fig. 1 features；Its elementary analysis
Chemical composition is 0.15Na2O·56.9Al2O3·38.5SiO2·4.0P2O5；Specific surface area 348m2/ g, pore volume 0.99cm3/ g,
Average pore size 11.4nm.
Embodiment 4
This example illustrates the preparation for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
First by quantitative concentrations 90gAl2O3/ L Al2(SO4)3Solution is placed in beaker, with vigorous stirring by ammoniacal liquor dropwise
Add, until system pH=10.5, gelling temperature is 40 DEG C；Concentration 60gSiO is added under agitation2/ L waterglass,
70 DEG C are warming up to be aged 3 hours；Gained solid sediment is pressed into sediment（Butt）：HCl：H2O=1：0.08：10 weight ratio
Exchanged 30 minutes at 60 DEG C, filtering washing makes sodium oxide content be less than 0.3%；Then gained solid sediment is pressed into sediment
（Butt）：H2O=1：8 weight ratio mixes mashing with water, and by P2O5：Material butt=0.016：1 weight is than adding phosphorus
Acid, reacts 2 hours at 60 DEG C, and filtering washing produces the mesopore activity that the present invention is provided for 10 hours after dry at 120 DEG C
Material.It is designated as PAM-4.
PAM-4 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with Fig. 1 features；Its elementary analysis
Chemical composition is 0.12Na2O·50.2Al2O3·48.0SiO2·1.5P2O5；Specific surface area 289m2/ g, pore volume 0.64cm3/ g,
Average pore size 8.8nm.
Embodiment 5
This example illustrates the preparation for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
Preparation process be the same as Example 4.Wherein solid sediment presses P with phosphoric acid2O5：Material butt=0.03：1 weight ratio
Mix, reacted 2 hours at 60 DEG C, filtering, which is washed and dried in 120 DEG C, produces the mesoporous active materials of the invention provided for 10 hours.
It is designated as PAM-5.
PAM-5 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with Fig. 1 features；Its elementary analysis
Chemical composition is 0.11Na2O·55.4Al2O3·41.2SiO2·2.9P2O5；Specific surface area 331m2/ g, pore volume 0.89cm3/ g,
Average pore size 10.7nm.
Embodiment 6
This example illustrates the preparation for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
Preparation process be the same as Example 4.Wherein solid sediment presses P with phosphoric acid2O5：Material butt=0.05：1 weight ratio
Mix, reacted 1 hour at 80 DEG C, filtering washing is simultaneously dried 10 hours in 120 DEG C, be calcined at 600 DEG C and produce this hair in 2 hours
The mesoporous active materials of bright offer.It is designated as PAM-6.
PAM-6 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is as shown in Figure 1；Its elementary analysis
Chemical composition is 0.11Na2O·51.3Al2O3·43.2SiO2·4.9P2O5；Specific surface area 364m2/ g, pore volume 1.03cm3/ g,
Average pore size 11.3nm.
Comparative example 1
This comparative example illustrates the silica-alumina material that structure of similar to thin diaspore is prepared according to the process described in CN1565733A.
With concentration 90gAl2O3/ L Al2(SO4)3Solution and concentration 102gAl2O3/ L, Crater corrosion 1.7 NaAlO2Solution is
Reaction raw materials, cocurrent plastic simultaneously adjusts plastic pH=9.0, collects plastic slurries, concentration 60gSiO is proportionally added under stirring2/L
Waterglass, be warming up to 70 DEG C be aged 2 hours；Use NH4Cl solution presses sediment（Butt）：Ammonium salt：H2O=1:0.8:15 weight
Amount ratio, carries out ion exchange removing sodium ion at 60 DEG C to sial sediment, and exchange repeats twice, and 0.5 is carried out every time
Hour, it is less than 0.3% to sodium oxide content, the mesopore sial produced described in CN1565733A for 10 hours is dried at 120 DEG C
Material.It is designated as DB-1.
DB-1 X-ray diffraction spectrogram is with Fig. 1 features；Its elementary analytical chemistry composition is 0.16Na2O·54.7Al2O3·
44.5SiO2；Specific surface area 329m2/ g, pore volume 0.82cm3/ g, average pore size 10.0nm.
Comparative example 2
This comparative example illustrates the mistake of the comparative sample obtained with conventional boehmite and silicon source and phosphorus source reaction modifying
Journey.
By a certain amount of industrial boehmite（Shandong Aluminum Plant, Al2O3Content 65wt%）By 1：15 weight ratio is mixed with water
Mashing is closed, stirring adds the watery hydrochloric acid of metering after 30 minutes, continue to add quantitative tetraethoxy-silicane after stirring 10 minutes, heat up
Reacted 4 hours to 80 DEG C, the phosphoric acid for adding metering continues to stir 1 hour, is then dried 10 hours at 120 DEG C, then at 550
Roasting obtains the comparative sample with structure of similar to thin diaspore in 4 hours at DEG C.It is designated as DB-2.
DB-2 X-ray diffraction spectrogram is as shown in Figure 2；Its elementary analytical chemistry composition is 0.08Na2O·50.1Al2O3·
45.2SiO2·4.2P2O5；Specific surface area 247m2/ g, pore volume 0.49cm3/ g, average pore size 7.5nm.
Embodiment 7
This example demonstrates that the cracking activity for the mesoporous active materials with structure of similar to thin diaspore that the present invention is provided.
By the mesoporous active materials in each embodiment and REY molecular sieves（RE2O316.5%, Na2O1.4%, Chang Ling catalyst plant
Production）By weight 1:9 ratio is mixed, and tabletting is simultaneously sieved into 20~40 mesh particles after grinding is uniform, 800 DEG C, 100%
Burin-in process 17 hours under water vapor conditions.Cracking performance evaluation is carried out on heavy oil microreactor, feedstock oil is pressure reduction gas
Oil, property is as shown in table 1.The micro- anti-appreciation condition of heavy oil is：Oil ratio 1.44, sample loading amount 2g, 500 DEG C of reaction temperature, then
Raw 600 DEG C of temperature.Evaluation result is listed in table 2 and table 3.
Comparative example 3
This comparative example illustrates the cracking activity of the comparative sample material of the gained of comparative example 1 and 2.
By the material DB-1 and DB-2 in comparative example 1 and 2 respectively with REY molecular sieves（RE2O316.5%, Na2O1.4%, Chang Ling
Catalyst plant is produced）By weight 1:9 ratio is mixed, and is designated as C-DB-1 and C-DB-2, and the uniform rear tabletting of grinding is simultaneously sieved
Into 20~40 mesh particles, burin-in process 17 hours, is split on heavy oil microreactor under 800 DEG C, 100% water vapor conditions
Change performance evaluation, the micro- anti-appreciation condition be the same as Example 7 of heavy oil.Evaluation result is listed in Table 2 below.
Table 1
Table 2
| Sample number into spectrum | C-1 | C-2 | C-3 | C-DB-1 | C-DB-2 |
| Added material | PAM-1 | PAM-2 | PAM-3 | DB-1 | DB-2 |
| Material balance/m% | |||||
| Dry gas | 2.11 | 2.08 | 2.16 | 2.10 | 1.82 |
| Liquefied gas | 9.37 | 9.47 | 9.62 | 9.42 | 9.46 |
| Gasoline | 43.12 | 45.57 | 44.74 | 41.73 | 39.46 |
| Diesel oil | 20.71 | 20.23 | 20.22 | 20.85 | 20.58 |
| Heavy oil | 16.00 | 13.75 | 14.41 | 17.24 | 19.94 |
| Coke | 8.69 | 8.90 | 8.85 | 8.65 | 8.74 |
| Conversion ratio/m% | 63.29 | 66.02 | 65.37 | 61.91 | 59.48 |
| Coke/conversion ratio | 0.137 | 0.135 | 0.135 | 0.140 | 0.147 |
Table 3
| Sample number into spectrum | C-4 | C-5 | C-6 |
| Added material | PAM-4 | PAM-5 | PAM-6 |
| Material balance/m% | |||
| Dry gas | 1.97 | 2.20 | 2.12 |
| Liquefied gas | 9.53 | 9.24 | 9.72 |
| Gasoline | 46.61 | 45.61 | 45.34 |
| Diesel oil | 20.55 | 20.67 | 20.15 |
| Heavy oil | 12.26 | 13.50 | 14.06 |
| Coke | 9.08 | 8.78 | 8.61 |
| Conversion ratio/m% | 67.19 | 65.83 | 65.79 |
| Coke/conversion ratio | 0.135 | 0.133 | 0.131 |
The mesopore activity of structure of similar to thin diaspore containing the present invention it can be seen from the heavy oil evaluation result of table 2 and table 3
The catalyst heavy oil cracking ability of material sample is stronger, and product distribution optimization, coke selectivity is more preferable.Its conversion ratio reaches
63.29m%~67.19m%, heavy oil yield is significantly reduced to below 16.00m%, and gasoline yield is improved to more than 43.12m%, burnt
Charcoal/conversion ratio ratio（Jiao turns ratio）Between 0.131~0.135, it is better than comparative sample.
Claims (18)
1. a kind of mesoporous active materials of boehmite crystal phase structure, it is characterised in that its anhydrous compound is constituted with oxide
Weight ratio meter is (0-0.2) Na2O·(50-86)Al2O3·(12-50)SiO2·(0.5-10)P2O5, the material specific surface area is
200~600m2/ g, pore volume is 0.5~1.8cm3/ g, average pore size is 8~18nm.
2. according to the material of claim 1, wherein, the material specific surface area is 250~550m2/ g, pore volume is 0.6~1.6cm3/
G, average pore size is 9~15nm.
3. according to the material of claim 1, it is characterised in that its anhydrous compound composition is calculated as (0-0.2) with oxide weight ratio
Na2O·(50-62)Al2O3·(38-50)SiO2·(0.5-5)P2O5, the material specific surface area is 200~400m2/ g, pore volume
For 0.5~1.2cm3/ g, average pore size is 8~15nm.
4. according to the material of claim 3, wherein, described specific surface area is 250~350m2/ g, pore volume is 0.6~1.0cm3/
G, average pore size is 9~12nm.
5. the preparation method of one of claim 1-4 active material, it is characterised in that including by silicon source and aqueous slkali in room temperature
Plastic is neutralized to 85 DEG C, it is 7~11 to control plastic pH value；According to SiO2：Al2O3=1：The weight of (1~7.5) is than adding silicon
Source, in room temperature to ageing at 90 DEG C 1~5 hour；Gained solid sediment and ammonium salt or acid solution contact are handled, are filtrated to get
Sodium content is less than 0.3% solid sediment；By obtained solid sediment and phosphorus source according to P2O5：Material butt=(0.005
~0.1)：1 weight is handled than contact, and in drying 10~20 hours at 100 DEG C~150 DEG C, or then at 500 DEG C~700 DEG C
Lower roasting 1~4 hour.
6. according to the preparation method of claim 5, wherein, SiO2：Al2O3=1：(1~1.7), P2O5：Material butt=(0.005
~0.05)：1.
7. according to the preparation method of claim 5, wherein, described silicon source is selected from aluminum nitrate, aluminum sulfate or aluminium chloride.
8. according to the preparation method of claim 5, wherein, described alkali is selected from ammoniacal liquor, potassium hydroxide, sodium hydroxide, or, institute
The alkali said is replaced with sodium metaaluminate.
9. according to the preparation method of claim 5, wherein, described silicon source is selected from sodium metasilicate, tetramethoxy-silicane, tetraethoxy
Silicon, tetrapropoxy-silicane, four butoxy silicon or silica.
10. according to the preparation method of claim 5, wherein, described to be handled with ammonium salt contact, its process is that ageing gained is solid
Body sediment presses the butt of sediment：Ammonium salt：H2O=1：(0.1~1)：The weight ratio of (5~30) is in room temperature to friendship at 100 DEG C
Change.
11. according to the preparation method of claim 10, described to be handled with ammonium salt contact, its process is carried out 1~3 time, is handed over every time
Change 0.5~1 hour, until sodium content is less than 0.3% in solid sediment.
12. according to the preparation method of claim 5,10 or 11, wherein, described ammonium salt is selected from ammonium chloride, ammonium sulfate, nitric acid
One or more in ammonium, ammonium carbonate and ammonium hydrogen carbonate.
13. according to the preparation method of claim 5, wherein, the described process that processing is contacted with acid solution is by ageing gained
Solid sediment press sediment butt：Acid：H2O=1：(0.03~0.3)：The weight ratio of (5~30) is in room temperature to 100 DEG C
Under at least exchange 0.2 hour.
14. according to the preparation method of claim 5 or 13, wherein, described acid is selected from sulfuric acid, hydrochloric acid or nitric acid.
15. according to the preparation method of claim 5, wherein, described to be handled with phosphorus source contact, its process is to be less than sodium content
0.3 weight % solid sediment is 1 by the butt and water of solid sediment：The weight of (5~20) is beaten than mixing, then by phosphorus
Source is added to be handled in slurries in room temperature to contact at 90 DEG C, is dried after filtering, washing at 100 DEG C~150 DEG C, and optionally,
It is calcined at 500 DEG C~700 DEG C.
16. according to the preparation method of claim 5, wherein, described to be handled with phosphorus source contact, its process is to be less than sodium content
0.3 weight % solid sediment is directly mixed with phosphorus source, is dried after grinding is uniform at 100 DEG C~150 DEG C, and optionally,
It is calcined at 500 DEG C~700 DEG C.
17. according to the preparation method of claim 5,15 or 16, wherein, described phosphorus source is selected from ammonium phosphate, diammonium hydrogen phosphate, phosphorus
Acid dihydride ammonium or phosphoric acid.
18. the mesoporous active materials of one of Claims 1 to 4 are applied in RFCC, catalyst or auxiliary agent are used as
Active component or active matrix material.
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