CN104588054B - A kind of mesoporous catalysis material of phosphorous and rare earth - Google Patents
A kind of mesoporous catalysis material of phosphorous and rare earth Download PDFInfo
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Abstract
The mesoporous catalysis material of a kind of phosphorous and rare earth, with typical boehmite crystal phase structure, its anhydrous compound composition is calculated as with oxide weight ratio（0‑0.2）Na2O·（40‑85）Al2O3·（10‑55）SiO2·（0.5‑10）P2O5·（0.5‑10）RE2O3, wherein there is special matching relationship between phosphorus and rare earth, the specific surface area of the material is 200~500m2/ g, pore volume is 0.5~1.5cm3/ g, average pore size is 8~18nm.The characteristics of catalysis material has mesoporous material, size range with reaction raw materials heavy oil macromolecular is suitable, the different compound proportions of phosphorus and rare earth component have certain adjustment effect to Acid Materials Acidic and catalysis activity so that material has more excellent heavy oil conversion performance and coke selectivity.
Description
Technical field
The present invention relates to a kind of mesoporous catalysis material, the in particular to mesoporous catalysis material of a kind of phosphorous and rare earth
Material.
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, generally the catalysis material with high cracking activity is needed to use in these courses of reaction
Material.
Micro-pore zeolite catalysis material has excellent shape selective catalysis performance and cracking reaction activity very high due to it, wide
It is applied in petroleum refining and processing industry generally.With increasingly exhausting for petroleum resources and wanting for the aspect such as environmental protection
Ask, particularly crude oil becomes the growth trend of weight increasingly（>500 DEG C of high boiling component increases）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 with 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 to reduce, 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 with the material compared with high cracking activity.It is and traditional micro porous molecular sieve is only beneficial to the cracking of small molecule therefore 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 molecular sieve analog hole wall structure be undefined structure, therefore hydrothermal stability difference and acidity is weaker, it is impossible to meet catalysis and split
The operating condition of change, commercial Application is very restricted.
Poor to solve the problems, such as mesopore molecular sieve hydrothermal stability, 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 the weaker shortcoming of acidity 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 the hydrothermally stable of highly acid and superelevation
Property.But the deficiency of this molecular sieve is that need to use expensive template, and aperture only has 2.7nm or so, for big point
Sub- cracking reaction still has larger space steric effect, and structure is easily collapsed under high temperature hydrothermal condition, 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, and for the preparation of new catalyst provides possibility, collect current result of study more
In using expensive organic formwork agent and organic silicon source, and majority will be by 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 load silicon oxide particle or the hydrated silica on porous boehmite, then by gained
Compound is obtained the silica supported catalyst on class boehmite surface, this material in more than 600 DEG C hydro-thermal process
Surface area be 100~200m2/ g, 7~7.5nm of average pore size.Serial acid Cracking catalyst is disclosed in US4440872,
The carrier of some of them catalyst is by γ-Al2O3Upper dipping silane, then makes after 500 DEG C of roastings or steam treatment
.US2394796 discloses dipping silicon tetrachloride or the silicon tetraethyl on porous hydrated alumina, then obtains sial through hydrolysis
Composite.It is raw material that inorganic aluminate and waterglass are used in CN1353008, and it is clear to form stabilization 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.A kind of mesoporous silica-alumina materials are disclosed in CN1565733A, the silica-alumina material has boehmite crystal phase structure,
Pore-size distribution is concentrated, specific surface area about 200~400m2/ g, 0.5~2.0ml/g of pore volume, average pore size most may be used between 8~20nm
Several apertures are 5~15nm.The preparation of the mesoporous silica-alumina materials is without the use of organic formwork agent, synthesizes low cost, the sial for obtaining
Material has cracking activity and hydrothermal stability high, and good macromolecular cracking performance is shown in catalytic cracking reaction.
US6858555 discloses a kind of catalyst for cracking heavy oil containing mixed-metal oxides such as sieve and silica-sesquioxide, wherein sial oxygen
Compound is undefined structure.One kind is disclosed in CN1138566 and is dispersed with silicon, boron, phosphorous oxides, VIII and group vib metal oxygen
The mesoporous alumina gel of compound, it mainly uses organic silicon source, silicon source, boron source and soluble sources for raw material and is dissolved in organic
In alcoholic solution, add organic formwork agent and be hydrolyzed and gelation, gained mesoporous gel can be used as catalyst carrier, acid catalysis
Agent or hydrogenation catalyst are used.
The content of the invention
The purpose of the present invention is the mesoporous catalysis material for providing a kind of phosphorous and rare earth on the basis of existing technology, the material
There is good heavy oil conversion performance when expecting for during catalytic cracking reaction.
The mesoporous catalysis material of the phosphorous and rare earth that the present invention is provided, with typical boehmite crystal phase structure, its
Anhydrous compound composition is calculated as with oxide weight ratio（0-0.2）Na2O·（40-85）Al2O3·（10-55）SiO2·（0.5-
10）P2O5·（0.5-10）RE2O3, the specific surface area of the material is 200~500m2/ g, preferably 300~450m2/ g, pore volume is
0.5~1.5cm3/ g, preferably 0.7~1.2cm3/ g, average pore size is 8~18nm, preferably 10~15nm.Described RE represents lanthanum
One or more rare earth in system, usually using lanthanum, cerium mischmetal or pure lanthanum rare earth in catalytic cracking, pure cerium mischmetal is less
Use, lanthanum cerium with market situation than that can be varied from mischmetal, but performance is not influenceed by mixed proportion substantially.It is described
Rare earth be preferably lanthanum, cerium or the mischmetal containing lanthanum and cerium.
The mesoporous catalysis material of the phosphorous and rare earth described in the present invention, through the following steps that prepare, specific step
It is rapid as follows：
（1）By silicon source and aqueous slkali in room temperature to plastic is neutralized at 85 DEG C, it is 7~11 control plastic pH value；
（2）According to SiO2：Al2O3=1：（0.6~9）Weight than adding silicon source, it is small to ageing 1~5 at 90 DEG C in room temperature
When；
（3）Gained solid sediment and ammonium salt or acid solution contact are processed, sodium content is filtrated to get less than 0.3 weight %
Solid sediment；
（4）By step（3）One or more metallic compound in the solid sediment and phosphorus source and group of the lanthanides that obtain, according to
P2O5：RE2O3：Material butt=（0.005~0.1）：（0.005~0.1）：1 weight is processed than contact, and in 100 DEG C~150
Dried 10~20 hours at DEG C, or be calcined 1~4 hour at 500 DEG C~700 DEG C.
In described preparation process, step（1）The silicon source for being used includes aluminum nitrate, aluminum sulfate or inorganic aluminum etc. aluminium chloride
Any one in source；The alkali for being used includes any one in ammoniacal liquor, potassium hydroxide, NaOH or sodium metaaluminate；Step（2）
The silicon source for being used includes waterglass, sodium metasilicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon or oxygen
Any one in SiClx.
In described preparation process, step（3）The described process that treatment is contacted with ammonium salt, is those skilled in the art institute
Know, typically by step（2）The solid sediment of gained presses sediment butt：Ammonium salt：H2O=1：（0.1~1）：（5~30）
Weight ratio in room temperature to exchanging at 100 DEG C 1~3 time, exchange 0.5~1 hour every time, until sodium content is low in solid sediment
In 0.3%.During described ammonium salt contact treatment, ammonium salt includes ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate
In one or more.
In described preparation process, step（3）The described process that treatment is contacted with acid solution, is by step（2）Gained
Solid sediment press sediment butt：Acid：H2O=1：（0.03~0.30）：（5~30）Weight ratio in room temperature to 100 DEG C
Under at least exchange 0.2 hour.The acid used during described acid solution contact treatment usually inorganic acid, can be selected from sulphur
Acid, hydrochloric acid or nitric acid.
In described preparation process, step（4）It is described with phosphorus source and group of the lanthanides in one or more metallic compound
Contact processing procedure can have various, including：
By step（3）Gained solid sediment presses sediment butt：H2O=1：（5~20）Weight ratio mix with water beat
Slurry, then one or more metallic compound in phosphorus source and group of the lanthanides is added in above-mentioned slurries one or more times, in room temperature
At to 90 DEG C contact treatment 0.2~5 hour, preferably 0.5~3 hour, filtering washing after at 100 DEG C~150 DEG C dry 10~
20 hours；
Or by step（3）Gained solid sediment presses sediment butt：H2O=1：（5~20）Weight ratio and water mix
Mashing is closed, then one or more metallic compound in phosphorus source or group of the lanthanides is added in above-mentioned slurries, in room temperature at 90 DEG C
Contact treatment 0.2~5 hour, preferably 0.5~3 hour, after filtering directly with group of the lanthanides in one or more metallic compound or
Phosphorus source mixes in proportion, is dried 10~20 hours at 100 DEG C~150 DEG C after grinding is uniform；
Or by step（3）Gained solid sediment is directly pressed with one or more metallic compound in phosphorus source or group of the lanthanides
Ratio mixes, and is dried 10~20 hours at 100 DEG C~150 DEG C after grinding is uniform, is not calcined or is roasted at 500 DEG C~700 DEG C
Burn 1~4 hour；Then add water again and be beaten and mix with one or more metallic compound or phosphorus source in group of the lanthanides, in room temperature
At to 90 DEG C contact treatment 0.2~5 hour, preferably 0.5~3 hour, filtering washing after at 100 DEG C~150 DEG C dry 10~
20 hours；
Or by step（3）Gained solid sediment is directly pressed with one or more metallic compound in phosphorus source and group of the lanthanides
Ratio mixes, and is dried 10~20 hours at 100 DEG C~150 DEG C after grinding is uniform.Above-mentioned dried sample can not be calcined or
It is calcined 1~4 hour at 500 DEG C~700 DEG C.Step（4）The phosphorus source for being used can be ammonium phosphate, diammonium hydrogen phosphate, phosphoric acid
Any one in ammonium dihydrogen or phosphoric acid.Metallic compound in the group of the lanthanides for being used can be any one water miscible chemical combination
Thing, such as nitrate, hydrochloride, such as lanthanum nitrate, lanthanum chloride, mixed chlorinated rare earth, lanthanum cerium is than typically with city in mischmetal
Situation and become, majority is between 4:6~6:Between 4.
The characteristics of phosphorous and rare earth catalysis material provided by the present invention has mesoporous material, average pore size 2~
50nm scopes, the size range with reaction raw materials heavy oil macromolecular is suitable, and the different compound proportions of phosphorus and rare earth component are to material
Acid and catalysis activity has certain adjustment effect so that material cracking activity is higher, heavy oil conversion performance enhancing, and product
Distribution more optimizes.The catalysis material can apply in catalytic cracking process, used as the work of heavy oil reforming catalyst or auxiliary agent
Property component or host material
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of the mesoporous catalysis material of embodiment 1.
Specific embodiment
The following examples illustrate the present invention further, but content not thereby limiting the invention.
In embodiments, Na in sample2O、Al2O3、SiO2、P2O5、RE2O3Content determined with x-ray fluorescence method（Ginseng
See《Petrochemical Engineering Analysis method（RIPP experimental techniques）》, Yang Cui surely compile by grade, and Science Press, nineteen ninety publishes）.Sample thing phase
Determined using X-ray diffraction method.The specific surface area of sample, pore volume, average pore size are determined by nitrogen absorption under low temperature-desorption method.
Embodiment 1
Using interval cocurrent plastic mode, it is stirred vigorously lower by Al2(SO4)3Solution and NaAlO2Solution is mixed into
Glue, control system pH=9.0 collects quantitative plastic slurries and adds waterglass under agitation, is warming up to 70 DEG C of ageings 2
Hour；Gained solid sediment is pressed into sediment butt after filtering：Ammonium salt：H2O=1：0.8：12 weight ratio is handed at 60 DEG C
Change 1 hour, after filtering washing, then by sediment butt：H2O=1：10 weight ratio is by gained Na2O content consolidating less than 0.3%
Body sediment mixes mashing with water, and by P2O5：RE2O3：Material butt=0.010：0.025：1 weight than add phosphoric acid and
Mixed chlorinated rare earth（Lanthanum cerium compares 45:55）, to be reacted 2 hours at 70 DEG C, filtering washing was after dry 15 hours at 120 DEG C
The mesoporous catalysis material of the phosphorous and rare earth of offer of the present invention is provided.It is designated as PR-1.
PR-1 has typical boehmite crystal phase structure, and its X-ray diffraction spectrum is illustrated in Fig. 1；Its elementary analysis
Chemical composition is 0.13Na2O·58.9Al2O3·37.4SiO2·0.8P2O5·2.4RE2O3；Specific surface area 349m2/ g, pore volume
0.95cm3/ g, average pore size 10.9nm.
Embodiment 2
Preparation process is with embodiment 1, wherein first pressing P2O5：Material butt：H2O=0.020：1：10 weight ratio is by phosphoric acid
With Na2Solid sediment of the O content less than 0.3% and water mixing mashing, and in being reacted 1 hour at 60 DEG C, pressed again after filtering
RE2O3：Material butt：H2O=0.014：1：8 weight ratio mixes mixed chlorinated rare earth and sediment and water, at 60 DEG C
Reaction 1 hour, filtering washing obtains final product present invention offer for 2 hours after being dried 15 hours at 120 DEG C then at 600 DEG C of roastings
The mesoporous catalysis material of phosphorous and rare earth.It is designated as PR-2.
PR-2 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.08Na2O·65.2Al2O3·31.4SiO2·1.9P2O5·1.2RE2O3；Specific surface area 412m2/ g,
Pore volume 1.01cm3/ g, average pore size 9.8nm.
Embodiment 3
Preparation process is with embodiment 1, wherein first pressing P2O5：Material butt：H2O=0.016：1：8 weight ratio by phosphoric acid with
Na2Solid sediment of the O content less than 0.3% and water mixing mashing, and in being reacted 1 hour at 70 DEG C, RE is pressed after filtering again2O3：
Material butt=0.031：1 weight ratio directly mixes mixed chlorinated rare earth and sediment, and grinding is uniform after dry at 120 DEG C
Dry 15 hours, the mesoporous catalysis material of the phosphorous and rare earth of present invention offer is obtained final product within 4 hours then at 550 DEG C of roastings.It is designated as PR-3.
PR-3 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.10Na2O·70.2Al2O3·24.8SiO2·1.5P2O5·3.1RE2O3；Specific surface area 435m2/ g,
Pore volume 1.14cm3/ g, average pore size 10.5nm.
Embodiment 4
With Al2(SO4)3Solution and NaAlO2Solution is reaction raw materials, first by Al2(SO4)3Solution is placed in beaker, is heated up
To 45 DEG C, NaAlO is added with vigorous stirring2Solution, until system pH=10.0, collects plastic slurries and add metering
Waterglass, and be aged 3 hours in 60 DEG C；Gained solid sediment is pressed into sediment butt：NH4Cl：H2O=1：0.5：10 weight
Than being exchanged 30 minutes at 50 DEG C, repeated exchanged once, is filtered after washing, by P amount2O5：La2O3：Material butt=0.027：
0.028：1 weight than directly mixes sediment with ammonium dihydrogen phosphate and lanthanum nitrate, and grinding is uniform after at 120 DEG C dry 10
Hour, the mesoporous catalysis material of the phosphorous and rare earth of present invention offer is provided for 4 hours then at 600 DEG C of roastings.It is designated as PR-4.
PR-4 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.06Na2O·60.8Al2O3·33.3SiO2·2.7P2O5·2.8La2O3；Specific surface area 370m2/ g,
Pore volume 0.89cm3/ g, average pore size 9.6nm.
Embodiment 5
Preparation process with embodiment 4, wherein by Na2Solid sediment of the O content less than 0.3% presses La2O3：Material butt：
H2O=0.018：1：8 weight ratio mixes with lanthanum nitrate and water, is stirred 1 hour at 70 DEG C, after filtering directly and ammonium dihydrogen phosphate
Mix in proportion, grinding is uniform after being dried 15 hours at 120 DEG C, and containing for present invention offer is obtained final product within 3 hours then at 550 DEG C of roastings
The mesoporous catalysis material of phosphorus and rare earth.It is designated as PR-5.
PR-5 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.12Na2O·68.5Al2O3·23.4SiO2·6.0P2O5·1.7La2O3；Specific surface area 408m2/ g,
Pore volume 1.10cm3/ g, average pore size 10.8nm.
Embodiment 6
Preparation process with embodiment 4, wherein by Na2Solid sediment of the O content less than 0.3% presses P2O5：Material butt：
H2O=0.035：1：10 weight ratio mixes with phosphoric acid and water, is stirred 1 hour at 70 DEG C, and drying 10 is small at 120 DEG C after filtering
When, then mix in proportion with mixed chlorinated rare earth solution, grinding is uniform after being dried 15 hours at 120 DEG C, then at 600 DEG C of roastings
The mesoporous catalysis material of the phosphorous and rare earth of present invention offer is provided for 3 hours.It is designated as PR-6.
PR-6 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.10Na2O·50.7Al2O3·41.0SiO2·3.4P2O5·4.6RE2O3；Specific surface area 319m2/ g,
Pore volume 0.98cm3/ g, average pore size 12.3nm.
Embodiment 7
By Al2(SO4)3Solution is placed in beaker, and stirring is lower to add ammoniacal liquor, until system pH=9.0, collect it is quantitative into
Waterglass is added under the stirring of rubber cement liquid, 60 DEG C is warming up to and is aged 2 hours；Gained solid sediment is pressed into sediment butt：
HCl：H2O=1：0.08：10 weight ratio is exchanged 1 hour at 50 DEG C, and filtering washing makes Na2O content is less than 0.3%；By filter cake
Directly mix with mixed chlorinated rare earth solution, grinding is uniform after 120 DEG C of dryings 10 hours；Then by dried sample again
It is beaten and mixes in proportion with phosphoric acid, stirred 1 hour at 70 DEG C, filtration drying obtains final product the present invention in 2 hours after 550 DEG C of roastings
The mesoporous catalysis material of the phosphorous and rare earth for providing.It is designated as PR-7.
PR-7 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.11Na2O·72.4Al2O3·21.2SiO2·0.6P2O5·5.3RE2O3；Specific surface area 396m2/ g,
Pore volume 0.96cm3/ g, average pore size 9.7nm.
Embodiment 8
Preparation process with embodiment 7, wherein by Na2O content less than 0.3% solid sediment directly in proportion with phosphoric acid
Mix, grinding is uniform after 120 DEG C of dryings 10 hours；Then dried sample is mixed in proportion with mixed chlorinated rare earth again
Close, then at 120 DEG C of dryings 10 hours after grinding is uniform, finally at 600 DEG C roasting obtain final product within 4 hours the phosphorous of present invention offer and
The mesoporous catalysis material of rare earth.It is designated as PR-8.
PR-8 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 1；Its element
Analytical chemistry composition is 0.13Na2O·74.6Al2O3·14.9SiO2·5.6P2O5·4.2RE2O3；Specific surface area 428m2/ g,
Pore volume 1.20cm3/ g, average pore size 11.2nm.
Comparative example
With Al2(SO4)3Solution and NaAlO2Solution is reaction raw materials, and cocurrent plastic simultaneously adjusts plastic pH=10.5, is collected
A certain amount of plastic slurries, are proportionally added into waterglass with vigorous stirring, are warming up to 70 DEG C and are aged 2 hours；Use NH4Cl solution is pressed
Sediment butt：Ammonium salt：H2O=1:0.8:15 weight ratio, carries out ion exchange removing sodium at 60 DEG C to solid sediment
Ion, by Na2The filter cake that O is washed till less than 0.3% adds water mashing again, then mixes with phosphoric acid in proportion, is warming up to 60 DEG C of stirrings 1
Hour, filtering obtains final product contrast material in 10 hours after drying at 120 DEG C.It is designated as DB-1.
DB-1 has structure of similar to thin diaspore, the same Fig. 1 of its X-ray diffraction spectrogram；Its elementary analytical chemistry is constituted
0.10Na2O·67.3Al2O3·28.9SiO2·3.4P2O5；Specific surface area 398m2/ g, pore volume 1.04cm3/ g, average pore size
10.5nm。
Embodiment 9
This example demonstrates that the cracking activity of the mesoporous catalysis material that the present invention is provided.
By the material in phosphorous and rare earth the mesoporous catalysis material and comparative example in each embodiment and REUSY molecular sieves
By weight 1：9 ratio is mixed, and the uniform rear compressing tablet of grinding is simultaneously sieved into 20~40 mesh particles, in 800 DEG C, 100% vapor
Under the conditions of burin-in process 17 hours.
Cracking performance evaluation is carried out on heavy oil microreactor, the micro- anti-appreciation condition of heavy oil is：Oil ratio 1.44, sample
Loading amount 2g, 500 DEG C of reaction temperature, 600 DEG C of regeneration temperature, feedstock oil is vacuum gas oil (VGO).Raw material oil nature is as shown in table 1.Comment
Valency result is listed in table 2 and table 3.
Be can be seen that containing its cracking activity of mesoporous catalysis material provided by the present invention more from the result of table 2 and table 3
Height, heavy oil conversion performance enhancing, and product slates more optimize, and the conversion ratio of C-1~C-8 is in 69.22~71.75m%, heavy oil
Below 11.27m% is reached, and the conversion ratio of comparative sample C-DB is 12.42m% in 67.61m%, heavy oil.
Table 1
Table 2
| Sample number into spectrum | C-1 | C-2 | C-3 | C-4 |
| Added material | PR-1 | PR-2 | PR-3 | PR-4 |
| Material balance/m% | ||||
| Dry gas | 1.84 | 1.81 | 1.83 | 1.82 |
| Liquefied gas | 9.84 | 10.85 | 9.79 | 11.05 |
| Gasoline | 47.55 | 47.24 | 48.84 | 47.21 |
| Diesel oil | 19.51 | 19.67 | 19.41 | 19.21 |
| Heavy oil | 11.27 | 10.64 | 10.03 | 11.10 |
| Coke | 9.99 | 9.79 | 10.10 | 9.61 |
| Conversion ratio/m% | 69.22 | 69.69 | 70.56 | 69.69 |
| Yield of light oil/m% | 67.06 | 66.91 | 68.25 | 66.42 |
| Coke/conversion ratio | 0.144 | 0.140 | 0.143 | 0.138 |
Table 3
| Sample number into spectrum | C-5 | C-6 | C-7 | C-8 | C-DB |
| Added material | PR-5 | PR-6 | PR-7 | PR-8 | DB-1 |
| Material balance/m% | |||||
| Dry gas | 1.85 | 1.84 | 1.90 | 1.86 | 1.78 |
| Liquefied gas | 10.29 | 9.49 | 10.62 | 10.14 | 9.37 |
| Gasoline | 49.35 | 48.02 | 47.80 | 47.72 | 46.52 |
| Diesel oil | 19.27 | 19.73 | 19.33 | 19.35 | 19.97 |
| Heavy oil | 8.98 | 10.80 | 10.64 | 10.93 | 12.42 |
| Coke | 10.26 | 10.12 | 9.71 | 10.00 | 9.94 |
| Conversion ratio/m% | 71.75 | 69.47 | 70.03 | 69.72 | 67.61 |
| Yield of light oil/m% | 68.62 | 67.75 | 67.13 | 67.07 | 66.49 |
| Coke/conversion ratio | 0.143 | 0.145 | 0.139 | 0.143 | 0.147 |
Claims (10)
1. the mesoporous catalysis material of a kind of phosphorous and rare earth for heavy oil conversion, with typical boehmite crystalline phase knot
Structure, its anhydrous compound composition is calculated as (0-0.2) Na with oxide weight ratio2O·(40-85)Al2O3·(10-55)SiO2·
(0.5-10)P2O5·(0.5-10)Re2O3, the specific surface area of the material is 200~500m2/ g, pore volume is 0.5~1.5cm3/ g,
Average pore size is 8~18nm.
2. according to the catalysis material of claim 1, wherein, the specific surface area of described material is 300~450m2/ g, pore volume is
0.7~1.2cm3/ g, average pore size is 10~15nm.
3. the preparation method of the catalysis material for heavy oil conversion of claim 1, including step is as follows：
(1) by silicon source and aqueous slkali in room temperature to plastic is neutralized at 85 DEG C, it is 7~11 control plastic pH value；
(2) according to SiO2：Al2O3=1：The weight ratio of (0.6~9) adds silicon source, in room temperature to ageing at 90 DEG C 1~5 hour；
(3) gained solid sediment and ammonium salt or acid solution contact are processed, is filtrated to get sodium content consolidating less than 0.3 weight %
Body sediment；
(4) one or more metallic compound in the solid sediment for obtaining step (3) and phosphorus source and group of the lanthanides, according to following
One kind and P during (i), (ii), (iii)2O5：Re2O3：Material butt=(0.005~0.1)：(0.005~0.1)：1
Weight than contact process；
I step (3) gained solid sediment is pressed sediment butt by ()：H2O=1：The weight ratio of (5~20) mixes mashing with water,
One or more metallic compound in phosphorus source and group of the lanthanides is added in above-mentioned slurries one or more times again, in room temperature to 90
Contact is processed at least 0.2 hour at DEG C, is dried 10~20 hours at 100 DEG C~150 DEG C after filtering washing；
(ii) step (3) gained solid sediment is pressed into sediment butt：H2O=1：The weight ratio of (5~20) mixes with water to be beaten
Slurry, then one or more metallic compound in phosphorus source or group of the lanthanides is added in above-mentioned slurries, in room temperature to contact at 90 DEG C
Treatment at least 0.2 hour, directly mixes after filtering with one or more metallic compound or phosphorus source in group of the lanthanides, after grinding is uniform
Dried 10~20 hours at 100 DEG C~150 DEG C, in roasting 1~4 hour at 500 DEG C~700 DEG C；
(iii) step (3) gained solid sediment is directly mixed with one or more metallic compound in phosphorus source or group of the lanthanides,
Dried 10~20 hours at 100 DEG C~150 DEG C after grinding is uniform, be calcined 1~4 hour at 500 DEG C~700 DEG C；Then weigh
New adding water is beaten and mixes with one or more metallic compound or phosphorus source in group of the lanthanides, is processed in room temperature to contact at 90 DEG C
At least 0.2 hour, dried 10~20 hours at 100 DEG C~150 DEG C after filtering washing.
4. according to the method for claim 3, wherein, the silicon source described in described step (1) is selected from aluminum nitrate, aluminum sulfate or chlorination
Aluminium；Described alkali is selected from ammoniacal liquor, potassium hydroxide or NaOH；Silicon source described in step (2) is selected from waterglass, sodium metasilicate, four
Methoxyl group silicon, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon or silica.
5. according to the method for claim 3, wherein, the alkali described in described step (1) is substituted with sodium metaaluminate.
6. according to the method for claim 3, wherein, the process that treatment is contacted with ammonium salt described in described step (3), is by step
Suddenly the solid sediment obtained by (2) presses sediment butt：Ammonium salt：H2O=1：(0.1~1)：The weight ratio of (5~30) is in room temperature
Exchanged 1~3 time to 100 DEG C, exchanged at least 0.5 hour every time, until sodium content is less than 0.3 weight % in solid sediment.
7. according to the method for claim 3, wherein, during described ammonium salt contact treatment, ammonium salt be selected from ammonium chloride, ammonium sulfate,
One or more in ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate.
8. according to the method for claim 3, wherein, described in described step (3) contacted with acid solution treatment process, be by
Solid sediment obtained by step (2) presses sediment butt：Acid：H2O=1：(0.03~0.30)：The weight ratio of (5~30) exists
Room temperature is at least exchanging 0.2 hour at 100 DEG C.
9. according to the method for claim 3, wherein, the acid used during described acid solution contact treatment is selected from sulfuric acid, salt
Acid or nitric acid.
10. the catalysis material of claim 1 or 2 is applied in catalytic cracking process, used as heavy oil reforming catalyst or auxiliary agent
Active component or host material.
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