CN104667996B9 - Hydrocracking catalyst carrier and preparation method thereof - Google Patents
Hydrocracking catalyst carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst carrier and a preparation method thereof, wherein the carrier comprises β molecular sieves, amorphous silica-alumina and alumina, wherein the properties of the used β molecular sieves are as follows2/Al2O3The carrier is prepared by kneading and molding β molecular sieve, amorphous silica-alumina and alumina, wherein the β molecular sieve with uniform framework silica-alumina structure and the amorphous silica-alumina are used as cracking components, and the prepared catalyst is used in the hydrocracking process and has the characteristics of high activity and high yield of low-freezing diesel oil.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, a kind of high activity, carrier of hydrocracking catalyst of Low Freezing Point diesel oil and preparation method thereof are particularly well-suited to.
Background technology
Hydrocracking technology has that adaptability to raw material is strong, products scheme flexibility is big, purpose product selectivity high, good product quality, added value high the features such as, various heavys, inferior raw material can be converted directly the industrial chemicals of clean fuel oil and high-quality, one of modern oil refining and the most important heavy oil deep processing technique of petro chemical industry are turned into, increasingly extensive application have been obtained in countries in the world.Because crude quality is deteriorated year by year, sour crude is significantly increased, and to oil refining process in itself and petroleum product-quality requirement is increasingly strict, market is continuously increased to clean fuel oil and industrial chemicals demand for environmental protection.Therefore, hydrocracking technology will be also more widely applied, while also itself proposes requirement higher to hydrocracking technology.
It is applied in Cracking catalyst play the key component mostly Y type molecular sieve and beta-molecular sieve of cracking.Relative to Y type molecular sieve, beta-molecular sieve has three-dimensional twelve-ring pore structure, but without the supercage structure as Y type molecular sieve, its double 6 yuan of rings unit bug hole structure for being mainly characterized by two 4 yuan of rings and four 5 yuan of rings, belong to cubic system, main channel diameter is in 0.56-0.75nm.Beta-molecular sieve has topological structure and stereoscopic three-dimensional duct feature so that it has effect well in cracking reaction to the fracture of chain hydrocarbon-selective, and with very strong isomery performance, can be used for Low Freezing Point intermediate oil as cracking component, be industrially widely used.
Beta-molecular sieve silicon-aluminum structure has diversity and complexity.The skeleton structure of beta-molecular sieve is more complicated compared to Y type molecular sieve, two linear channels are mutually orthogonal and perpendicular to [001] direction in three cross one another pore canal systems, pore size is 0.57 nm × 0.75 nm, 3rd twelve-ring pore canal system is parallel to [001] direction, it is non-linear channels, pore size is 0.56
nm×0.65 nm；The complete beta-molecular sieve framework silicon-aluminum structure of crystallization there is also diversity, and framework silicon-aluminum structure is the main body that four-coordination structure and this structure account for sial existence form total in molecular sieve, and its basic structure is by the different Si of content（4Al）、Si（3Al）、Si（2Al）、Si（1Al）And Si（0Al）Construction unit is constituted, and with Si（3Al）And Si（2Al）Based on structure type；The non-framework aluminum of hexa-coordinate is also there is in other molecular sieve；There are different changes in the sial existing way and content of these various structures, in follow-up different modifying process so as to produce different catalytic performances.
The existing method of modifying to beta-molecular sieve（Such as CN1105646A）In, usually first carrying out ammonium and exchange removing sodium, then high-temperature roasting removes template（Organic amine）, then dealuminzation and constant pressure hydro-thermal process are carried out, can so increase substantially the silica alumina ratio of beta-molecular sieve.Especially high-temperature roasting is except the process of amine, especially emphasize that baking inphases take off amine in the patents such as CN99113577.6, CN01106042.5, so not only preparation process is complicated, and molecular sieve will first pass through ammonium salt exchange sodium before ammonium is burnt in segmentation, sodium ion is for the negative electrical charge in balance molecule sieve skeleton frame（Generally framework aluminum is formed）, and the burning ammonium treatment carried out again after removing sodium（Either a step high-temperature process or multistep treatment of different temperature）To aggravate framework of molecular sieve dealuminzation, and there is non-selectivity framework dealumination, make the skeleton structure heterogeneity of modified molecular sieve, there is very big defect, and the non-framework aluminum structure of substantial amounts of hexa-coordinate is formd in duct（Duct is blocked, skeleton acid site is partly sheltered, non-ideal cracking reaction easily occurs）And follow-up acid treatment or hydro-thermal process, to all continue further to destroy the skeleton structure of molecular sieve, make to exist in framework of molecular sieve structure in the different Si of ratio (X-Al) structures and molecular sieve and there is a certain amount of non-framework aluminum structure, so that molecular sieve has varying strength acid site, different cracking performances are shown, the selectivity of catalyst purpose product will be largely effected on.Just because of the complexity of silicon-aluminum structure in beta-molecular sieve, modified framework of molecular sieve structure heterogeneity is caused using different method of modifying in the above method, directly affect the acid strength and sour density of modified molecular screen, and then influence the performance of catalyst.
A kind of method of modifying of beta-molecular sieve is disclosed in CN101450318A.The method is that sodium form beta-molecular sieve is exchanged with ammonium salt, the solution with phosphorus-containing compound solution and containing transistion metal compound carries out impregnating modified to molecular sieve again, the beta-molecular sieve for obtaining has the relative crystallinity of specific surface area and Geng Gao higher, further can generate low-carbon alkene by shape slective cracking.
CN01114175.1 discloses a kind of method of modifying of beta-molecular sieve.The method process is as follows：（1）The complete beta-molecular sieve of crystallization directly carries out ammonium salt exchange,（2）Beta-molecular sieve after ammonium salt is exchanged is filtered, washed, being dried and being calcined,（3）Beta-molecular sieve after the de- ammonium of roasting carries out acid treatment, filtering,（4）The complete beta-molecular sieve of acid treatment carries out pressurized thermal water treatment.In the method, acid treatment first is carried out to β zeolites, then hydro-thermal process is carried out again, it is using mineral acid treatment during acid treatment, the skeleton structure of moieties sieve will be destroyed in this course, molecular sieve crystallinity declines, the non-skeleton structure for forming bulk is stayed in molecular sieve pore passage, it is difficult to be removed, the acid distribution of influence modified molecular screen and acid strength, in addition, High-temperature water heat treatment has also been carried out after acid treatment, also a certain amount of non-framework aluminum can be formed in molecular sieve, this will directly affect the pore structure and Acidity of molecular sieve, the acid distribution and the change of Acidity of molecular sieve will directly affect thus performance of the molecular sieve as the catalyst of Cracking Component, especially influence is hydrocracked the property of diesel oil and chemical industry material.The step of other the method modified molecular screen, is more long, and the yield of molecules of interest sieve is relatively low in preparation process, while the modification of multi-step causes that modified cost and energy consumption are greatly improved.
US
5,350,501、US 5,447,623、US 5,279,726、US
5,536,687 describe a kind of catalyst containing beta-molecular sieve and Y molecular sieve.For producing during intermediate oil, consisting of：Y molecular sieve（1~15w%）, beta-molecular sieve（1~15w%）, decentralized sial, aluminum oxide, metal W and Ni.Beta-molecular sieve wherein used is that the mode for removing template through ion exchange and roasting obtains Hydrogen beta-molecular sieve.Catalyst reaction activity and middle distillates oil selectivity are all not bery high, it is difficult to meet manufacturer's aggrandizement apparatus disposal ability, further the need for volume increase intermediate oil.
CN1393521A discloses a kind of middle oil type hydrocracking catalyst and preparation method thereof, and catalyst used carrier is the complex type molecular sieve of amorphous silica-alumina, aluminum oxide and Y and β.Wherein composite molecular screen will be after mixing with modified Y molecular sieve after beta-molecular sieve original powder high temperature burning-off template, then through H+And NH4 +Mixed solution is processed and obtained.The method is by beta-molecular sieve original powder elder generation high temperature burning-off template, the skeleton structure of molecular sieve can so be influenceed, and the crystallinity of molecular sieve is greatly lowered, the acidity of molecular sieve is also influenceed simultaneously, the catalysis activity of catalyst prepared by this method is not high, and the product quality of the intermediate oil of boat coal and diesel oil still needs to further raising.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of carrier of hydrocracking catalyst and preparation method thereof.Carrier of the present invention is done as Cracking Component jointly by the beta-molecular sieve and amorphous silica-alumina of uniform framework silicon-aluminum structure, and with other components synergy, prepared catalyst is active high and the features such as voluminous low-coagulation diesel oil.
Carrier of hydrocracking catalyst of the present invention, comprising beta-molecular sieve, amorphous silica-alumina and aluminum oxide, the property of wherein beta-molecular sieve is as follows：
SiO2/Al2O3Mol ratio 30 ~ 150, preferably 40 ~ 150, more preferably 60 ~ 120, non-framework aluminum accounts for less than the 2% of total aluminium, and preferably less than 1%, with Si（0Al）The silicon atom of structural coordinates accounts for more than 95% of silicon atom in skeleton structure, preferably 95% ~ 99%, more preferably 96% ~ 99%.
In the present invention, described beta-molecular sieve, its property is preferably as follows：Relative crystallinity is 100% ~ 140%.
In the present invention, described beta-molecular sieve, its property is preferably as follows：Meleic acid amount is 0.1 ~ 0.5mmol/g, preferably 0.15 ~ 0.45mmol/g, NH3The acid amount of the middle strong acid that-TPD methods are measured accounts for more than the 80% of total acid content, preferably 80% ~ 95%, more preferably 85% ~ 95%.
In the present invention, described beta-molecular sieve, its property is preferably as follows：Na2O≤0.15wt%, preferably Na2O≤0.10wt%。
In the present invention, described beta-molecular sieve, its property is preferably as follows：Specific surface area is 400m2/g~800m2/ g, preferably 500 m2/g ~700m2/ g, total pore volume is 0.3mL/g ~ 0.50mL/g.
In beta-molecular sieve of the invention, total aluminium refers to the summation of the aluminium in aluminium and non-framework aluminum in molecular sieve middle skeleton aluminium.Non-framework aluminum refers to the aluminium existed with hexa-coordinate structure type in molecular sieve.Framework aluminum refers to the aluminium existed with four-coordination structure type in molecular sieve.Silicon atom in skeleton structure（Framework silicon atom）, i.e., with Si（4Al）、Si（3Al）、Si（2Al）、Si（1Al）And Si（0Al）The summation of the silicon atom of structural coordinates.Wherein, Si（4Al）、Si（3Al）、Si（2Al）、Si（1Al）And Si（0Al）It is the four-coordination structure from the silicon atom in silicon-oxy tetrahedron in different co-ordination states（That is skeleton structure）, Si（4Al）Refer to silicon atom in silicon-oxy tetrahedron be only joined directly together with 4 aluminum-oxygen tetrahedrons four-coordination structure i.e. Si [（OAl）4], Si（3Al）Refer to silicon atom and 3 aluminum-oxygen tetrahedrons in silicon-oxy tetrahedron and 1 silicon-oxy tetrahedron be joined directly together four-coordination structure i.e. Si [（OAl）3（OSi）1], Si（2Al）Be four-coordination structure that silicon atom and 2 aluminum-oxygen tetrahedrons in silicon-oxy tetrahedron and 2 silicon-oxy tetrahedrons are joined directly together refer to Si [（OAl）2（OSi）2], Si（1Al）Refer to silicon atom and 1 aluminum-oxygen tetrahedron in silicon-oxy tetrahedron and 3 silicon-oxy tetrahedrons be joined directly together four-coordination structure Si [（OAl）1（OSi）3], Si（0Al）Refer to silicon atom in silicon-oxy tetrahedron be only joined directly together with 4 silicon-oxy tetrahedrons four-coordination structure Si [（OSi）4]。
Amorphous silica-alumina used can be prepared by coprecipitation or grafting copolymerization process in catalyst of the present invention, be prepared by conventional method in document.SiO in obtained amorphous silica-alumina2Weight content be 5% ~ 40%, preferably 7% ~ 30%, the pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, and preferably 0.8 ~ 1.0mL/g, specific surface area is 300 ~ 500m2/ g, preferably 350 ~ 500m2/g。
Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of beta-molecular sieve is 3% ~ 20%, and the content of amorphous silica-alumina is 10% ~ 70%, preferably 25% ~ 55%, and the content of aluminum oxide is 15% ~ 70%, preferably 25% ~ 62%.
The specific surface area of carrier of hydrocracking catalyst of the present invention is 300 ~ 500m2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of carrier of hydrocracking catalyst of the present invention, comprises the following steps：
Then beta-molecular sieve, amorphous silica-alumina, aluminum oxide mechanical mixture, shaping are dried and be calcined, catalyst carrier is made；The wherein preparation method of beta-molecular sieve, including：
（1）Beta-molecular sieve original powder is contacted with normal pressure, dynamic water vapour, the temperature of contact is 500 ~ 650 DEG C, and the time is 5 ~ 10 hours；
（2）By step（1）The product of gained is contacted with ammonium fluosilicate, is then filtered, washes and is dried, and obtains beta-molecular sieve.
Step（1）Beta-molecular sieve original powder is synthesized using hydro-thermal method by template of organic amine, its SiO2/Al2O3Mol ratio 22.5 ~ 28.5, Na2O content is 1.0wt% ~ 3.0wt%.
Step（1）Beta-molecular sieve original powder is carried out in normal pressure, the treatment of dynamic water vapour condition, the general water vapour using flowing, and using 100wt% water vapours, water vapour passes through molecular screen primary powder by every kilogram of 50 ~ 100L/h of beta-molecular sieve original powder.
Step（2）In, by step（1）The product of gained is contacted with ammonium fluosilicate, its condition：40 ~ 120 DEG C of temperature, preferably 70 ~ 100 DEG C, the time is 0.5 ~ 8.0 hour, preferably 1.0 ~ 3.0 hours.Described washing conditions：It is general to be washed using deionized water, untill the close neutrality of cleaning solution pH value.Described drying condition is as follows：Dried 3 ~ 6 hours under conditions of 100 ~ 120 DEG C.
In catalyst carrier preparation method of the present invention, the drying of carrier and roasting generally in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then can be calcined 2.5 ~ 6.0 hours using conventional condition at 450 DEG C ~ 550 DEG C.
The features such as beta-molecular sieve that catalyst carrier of the present invention is used has uniform framework silicon-aluminum structure, acidity is suitable, pore structure is reasonable, suitably as Cracking Component, make catalyst that there is catalysis activity and isomerism ability higher, be suitable for producing the diesel product of low condensation point long distillate high-quality.
The inventive method needs not move through the preprocessing process such as ammonium exchange first using normal pressure, Dynamic Hydrothermal treatment molecular screen primary powder, can realize that molecular sieve takes off ammonium in the presence of dynamic high temperature water vapour（Template removal）Framework aluminum activation energy is reduced with selectivity, and avoid to framework of molecular sieve structural damage, and keep the homogeneity of framework of molecular sieve structure, it is engaged with follow-up ammonium hexafluorosilicate modifying process, effectively the framework aluminum of low energy can uniformly be deviate from, and silicon atom is supplemented on skeleton, make the skeleton structure of molecular sieve more homogeneous and stabilization, simultaneously, sodium ion in molecular sieve is also together carried over, sodium content in molecular sieve can be taken off below 0.15wt%, carry out in the prior art multistep ammonium exchange so as to overcome（Wash sodium）With high energy consumption, pollute it is big the shortcomings of.The inventive method by ammonium hexafluorosilicate can further unimpeded pore passage structure, the non-framework aluminum for producing can deviate from from molecular sieve pore passage, reached non-framework aluminum and made the more unobstructed purpose of molecular sieve pore passage.The present invention makes modified molecular sieve have reasonable uniform framework silicon-aluminum structure, pore structure, acid centre intensity and sour Density Distribution more uniform by optimizing method of modifying, is conducive to provide uniform cracking center, improves the purpose product selectivity of catalyst.
Catalyst carrier of the present invention is with beta-molecular sieve as acidic components, suitable amorphous silica-alumina is especially added for the second Cracking Component, its respective performance characteristics is given full play to, preferable concerted catalysis effect is generated again, make the hydrocracking catalyst that thus prepares while activity is improved, but be moderately hydrocracked with good selective opening of cyclic paraffins, isomerization of paraffinic hydrocarbons, heavy distillat, aromatic hydrocarbons saturation and hetero atom removing performance.Make the prepared active height of hydrocracking catalyst, can maximum production low freezing point diesel fuel, while the hydrogenation tail oil of high-quality can and be produced.
Brief description of the drawings
Fig. 1 is：Beta-molecular sieve of the present invention in embodiment 627Al MASNMR spectrograms, wherein abscissa are ppm；
Fig. 2 is：Molecular sieve is contrasted in comparative example 127Al MASNMR spectrograms, wherein abscissa are ppm.
Specific embodiment
Aluminum oxide can be using aluminum oxide used in conventional hydrocracking catalyst, such as macroporous aluminium oxide and ∕ or small porous aluminum oxide in carrier of hydrocracking catalyst of the present invention.0.7 ~ the 1.0mL/g of pore volume of macroporous aluminium oxide used, 200 ~ 500m of specific surface area2/g.The pore volume of small porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
The such as peptization acid of conventional shaping assistant, extrusion aid etc. can also be added in catalyst carrier preparation process of the present invention.
The preparation method of the beta-molecular sieve used by carrier of hydrocracking catalyst of the present invention, specifically includes following steps：
（1）Beta-molecular sieve original powder is contacted with normal pressure, dynamic water vapour, the temperature of contact is 500 ~ 650 DEG C, and the time is 5 ~ 10 hours；
（2）By step（1）The product of gained is contacted with ammonium fluosilicate, is then filtered, washes and is dried, and obtains beta-molecular sieve.
Step（1）In, preferably be placed in beta-molecular sieve original powder in container by the mode that beta-molecular sieve original powder is contacted with normal pressure, dynamic water vapour, then introduces water vapour from one end of container, is discharged from the other end of container by after beta-molecular sieve original powder.In order that molecular sieve treatment is evenly, preferably molecular sieve is placed in rotary container such as tube furnace, water vapour is gone out from the other end of container again after passing into molecular sieve from one end of container.Pressure in container keeps atmospheric pressure state, Contact Temperature to be maintained at 500 ~ 650 DEG C, and process time is 5 ~ 10 hours；
Under preferable case, step（1）Using temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, further preferably at 250 ~ 400 DEG C, starts to introduce water vapour, and is continuously heating to 500 ~ 650 DEG C, is then stopped 5 ~ 10 hours at this temperature.
Under preferable case, step（1）Beta-molecular sieve original powder is that it is template generally to use organic amine using conventional hydro-thermal method synthesis, and conventional organic amine template can be using one or more in tetraethyl ammonium hydroxide, TMAH, tetraethylammonium bromide etc..Template is usually contained in beta-molecular sieve original powder, and the weight content of template is generally 10% ~ 15%.The property of beta-molecular sieve original powder is as follows：SiO2/Al2O3Mol ratio 22.5 ~ 28.5, Na2O content is 1.0wt% ~ 3.0wt%.Template agent content can use differential scanning calorimetry in beta-molecular sieve original powder（DSC）- DTG（TG）Obtain, wherein DTG is using Germany's Netzsch companies STA449C-QMS403C type instruments, it is under an argon atmosphere, gas flow is 25mL/min, heating rate is 10 DEG C/min, temperature rises to 600 DEG C from room temperature, and sample quality about 10mg, the loss of weight amount for taking beta-molecular sieve original powder between 150 DEG C ~ 500 DEG C is calculated as the amount of template.
Step（1）In normal pressure, the treatment of dynamic water vapour condition, using 100wt% water vapours, water vapour passes through molecular screen primary powder to beta-molecular sieve original powder by every kilogram of 50 ~ 100L/h of beta-molecular sieve original powder.
Step（2）By step（1）The product of gained is contacted with ammonium fluosilicate.The condition of the contact includes：Temperature is 40 ~ 120 DEG C, and preferably 70 ~ 100 DEG C, the time is 0.5 ~ 8.0 hour, preferably 1.0 ~ 3.0 hours.
Under preferable case, step（2）Using the ammonium fluosilicate aqueous solution and step（1）The beta-molecular sieve contact of gained, the concentration of the ammonium fluosilicate aqueous solution is 10g ~ 60g/100mL solution, and the ammonium fluosilicate aqueous solution is 3 with the solid volume ratio of the liquid of beta-molecular sieve：1~15：1, preferably 4：1~10：1.
By step（2）Slurries after contact are directly filtered, and the filter cake after filtering again by washing for several times.Wherein described washing is general to be washed using deionized water, untill the close neutrality of cleaning solution pH value.Wash temperature can be 50 ~ 100 DEG C, and preferably 60 ~ 90 DEG C, the solid volume ratio of liquid is generally 5：1~15：1, wash time is 0.5 ~ 1.0 hour, with the close neutrality of cleaning solution pH value.The drying is dried 3 ~ 6 hours preferably under conditions of 100 ~ 120 DEG C.
The yield of the modified beta-molecular sieve of the inventive method is in more than 85wt%.
The following examples are used to illustrate in greater detail the present invention, but the scope of the present invention is not limited solely to the scope of these embodiments.In the present invention, wt% is mass fraction.
Heretofore described specific surface area is to use low temperature liquid nitrogen determination of adsorption method according to ASTM D3663-2003 standards.
Heretofore described pore volume is to use low temperature liquid nitrogen determination of adsorption method according to ASTM D4222-2003 standards.
In the present invention, NH3- TPD methods are a kind of methods of conventional measurement molecular sieve acid amount, and the instrument for using is Mike instrument company Auto-Chem
II 2920 type chemical adsorption instruments.Using ammonia as adsorption desorption medium, helium（Purity is 99.99v%）As carrier gas, acid amount i.e. weak acid amount, middle strong acid amount and strong acid amount and the total acid content in different desorption temperature areas is obtained using temperature programmed desorption and chromatography.Specific operation process is as follows：20 ~ 40 mesh sieve sample 0.1g are taken, in the presence of helium（Helium flow velocity is 30mL/min）, 500 DEG C are warming up to, then constant temperature 1 hour be down to 150 DEG C, constant temperature 5 minutes.Afterwards, ammonia is passed through until molecular sieve adsorption saturation, switches to helium and continuously purge（Helium flow velocity is 30mL/min）, programming rate is 10 DEG C/min, is heated up 250 DEG C, and constant temperature 1 hour is further continued for being warming up to 400 DEG C afterwards, and constant temperature 1 hour is further continued for being warming up to 500 DEG C, constant temperature 1 hour.In ammonia desorption process, ammonia is recorded by chromatograph and is desorbed spectrogram.In the ammonia desorption spectrogram of gained, three humidity provinces i.e. 150 DEG C ~ 250 DEG C, 250 DEG C ~ 400 DEG C, 400 DEG C ~ 500 DEG C acid amounts for corresponding to weak acid, middle strong acid and strong acid respectively are divided into by desorption temperature, the acid amount sum of weak acid, middle strong acid and strong acid is total acid content.Unit is measured in acid：Mmol/g, i.e., the ammonia amount of sieve absorption per gram molecule.
With pyridine as adsorbent, using infrared spectroscopic determination, instrument is the Fourier infrared spectrographs of NICOLET companies of U.S. Nicolet 6700 to meleic acid amount of the present invention, and its process is as follows：
Take levigate（Granularity is less than 200 mesh）Sample 20mg is pressed into the thin slice of a diameter of 20mm, on the specimen holder of absorption cell, takes 200mg samples（Sheet）Be fitted into quartz spring lower end hangs cup（Its length was recorded before sample-adding product,x 1, mm）, absorption cell and adsorption tube are connected, start to evacuate purification, vacuum is up to 4 × 10-2During Pa, 500 DEG C of holding 1h are warming up to, to remove the surface adsorbate of sample（Now, its length after sample purification is designated as,x 2, mm）.Then room temperature is down to, Adsorption of Pyridine is to saturation, then is warmed up to 160 DEG C, balance 1 hour, the pyridine of desorption physical absorption（Now, its length after Adsorption of Pyridine is designated as,x 3, mm）, try to achieve total acid content using pyridine weight adsorption, and the infrared spectrogram of gained under above-mentioned condition is recorded, the corresponding bands of a spectrum 1545cm of wherein B acid-1, the corresponding bands of a spectrum 1455cm of L acid-1, thus peak area ratio calculating B acid amount and the sour ratios measured of L according to each bands of a spectrum, obtain total acid content, B acid amount and L acid and measure；
Wherein total acid content is calculated using pyridine weight adsorption, specific as follows：
Hooke's law（Hooke's law）（Spring extended length and stress relation）：f=k△x
When spring is placed vertically：m=k△x
Wherein, m is sample quality, gram；△ x are spring extended length, mm；K is the spring coefficient of stiffiness.
Total acidC（Unit：MM/gram）：
Note：79.1 for pyridine molal weight, unit for gram/mol.
In the present invention, relative crystallinity (relative crystallinity) is determined using XRD method, and instrument is Rigaku Dmax-2500
X-ray diffractometer, using CukαRadiation, graphite monocrystalline filtering, operates tube voltage 35KV, tube current 40mA, sweep speed（2θ）It is 2 °/min, sweep limits is 4 ° -35 °.Standard specimen is the beta-molecular sieve original powder that the embodiment of the present invention 1 is used.
In the present invention, silica alumina ratio uses chemical method；Sodium content uses plasma emission spectrometry.
In the present invention, using nuclear magnetic resonance spectroscopy（NMR methods）Obtain27Al
MAS NMR spectras, so as to obtain the ratio of framework aluminum and non-framework aluminum, in terms of Al atoms.Using nuclear magnetic resonance spectroscopy（NMR methods）Obtain29Si
MAS NMR spectras, so as to obtain silicon atom with different co-ordination states（Si（4Al）、Si（3Al）、Si（2Al）、Si（1Al）And Si（0Al））The ratio that form is present, in terms of Si atoms.Nuclear magnetic resonance spectroscopy（NMR methods）It is using Bruker AVANCE
The type nuclear magnetic resonance spectrometers of III 500, wherein software use Topspin 2.0.Surveying29Accepted standard material is tetramethylsilane during Si MAS NMR spectras（TMS）, resonant frequency is 99MHz, experiment condition：4-6 microsecond pulse widths, 60-120 seconds relaxation delay.Surveying27Al
During MAS NMR spectras, accepted standard material is alchlor, and resonant frequency is 133MHz, experiment condition：4-6 microsecond pulse widths, 60-120 seconds relaxation delay.Gained29In Si MAS NMR spectras, Si（4Al）Corresponding chemical shift is -81 ~ -96ppm, Si（3Al）Corresponding chemical shift is -96 ~ -100ppm, Si（2Al）Corresponding chemical shift is -100 ~ -106ppm, Si（1Al）Corresponding chemical shift is -106 ~ -109ppm and Si（0Al）Corresponding chemical shift is -109 ~ -115ppm）.Gained27Al
In MAS NMR spectras, the corresponding chemical shift of framework aluminum is 40 ~ 65ppm, and the corresponding chemical shift of non-framework aluminum is -10 ~ 10ppm.
Embodiment 1
Take beta-molecular sieve original powder（It is that template is synthesized using hydro-thermal method with tetraethyl ammonium hydroxide, the weight content of template is about 11.8% in beta-molecular sieve original powder, is provided by Sinopec catalyst Fushun branch company）, its chemical SiO2/Al2O3Mol ratio is 25.5, Na2O content is 2.45wt%, in its skeleton structure, is passed through29Si
MAS NMR spectras, the distribution for obtaining the silicon atom that different co-ordination state forms are present is as follows：Si（4Al）It is 7.6%, Si（3Al）It is 30.6%, Si（2Al）It is 32.3%, Si（1Al）It is 21.0%, Si（0Al）It is 8.5%.Above-mentioned beta-molecular sieve original powder 1000g is taken, is fitted into tube furnace, using the method for temperature programming（Heating rate is 100 DEG C/h）, starting to introduce the water vapour of 100wt% when tubular type furnace temperature is raised to 300 DEG C, the flow of water vapour is 50L/ hours, and by diamond heating to 550 DEG C, constant temperature time is 6 hours.Gained molecular sieve numbering is BS-1.
Embodiment 2
Beta-molecular sieve original powder is taken with embodiment 1.Above-mentioned molecular sieve 1000g is taken, is fitted into tube furnace, using the method for temperature programming（Heating rate is 100 DEG C/h）, starting to introduce the water vapour of 100wt% when tubular type furnace temperature is raised to 300 DEG C, the flow of water vapour is 70L/ hours, and by diamond heating to 600 DEG C, constant temperature time is 8 hours.Gained molecular sieve numbering is BS-2.
Embodiment 3
Beta-molecular sieve original powder is taken with embodiment 1.Above-mentioned molecular sieve 1000g is taken, is fitted into tube furnace, using the method for temperature programming（Heating rate is 100 DEG C/h）, starting to introduce the water vapour of 100wt% when tubular type furnace temperature is raised to 300 DEG C, the flow of water vapour is 70L/ hours, and by diamond heating to 650 DEG C, constant temperature time is 10 hours.Gained molecular sieve numbering is BS-3.
Embodiment 4
Take beta-molecular sieve original powder（It is that template is synthesized using hydro-thermal method with tetraethyl ammonium hydroxide, the weight content of template is about 10.6% in beta-molecular sieve original powder, is provided by Sinopec catalyst Fushun branch company）, its chemical SiO2/Al2O3Mol ratio is 22.5, Na2O content is 2.35wt%, in its skeleton structure, is passed through29Si
MAS NMR spectras, the distribution for obtaining the silicon atom that different co-ordination state forms are present is as follows：Si（4Al）It is 7.7%, Si（3Al）It is 31.5%, Si（2Al）It is 30.9%, Si（1Al）It is 21.9%, Si（0Al）It is 8.0%.Above-mentioned beta-molecular sieve original powder 1000g is taken, is fitted into tube furnace, using the method for temperature programming（Heating rate is 80 DEG C/h）, starting to introduce the water vapour of 100wt% when tubular type furnace temperature is raised to 400 DEG C, the flow of water vapour is 80L/ hours, and by diamond heating to 600 DEG C, constant temperature time is 5 hours.Gained molecular sieve numbering is BS-4.
Embodiment 5
Take beta-molecular sieve original powder（It is that template is synthesized using hydro-thermal method with tetraethyl ammonium hydroxide, the weight content of template is about 13.2% in beta-molecular sieve original powder, is provided by Sinopec catalyst Fushun branch company）, its chemical SiO2/Al2O3Mol ratio is 28.5, Na2O content is 2.75wt%, in its skeleton structure, is passed through29Si
MAS NMR spectras, the distribution for obtaining the silicon atom that different co-ordination state forms are present is as follows：Si（4Al）It is 8.8%, Si（3Al）It is 28.7%, Si（2Al）It is 31.3%, Si（1Al）It is 23.5%, Si（0Al）It is 7.7%.Above-mentioned beta-molecular sieve original powder 1000g is taken, is fitted into tube furnace, using the method for temperature programming（Heating rate is 100 DEG C/h）, starting to introduce the water vapour of 100wt% when tubular type furnace temperature is raised to 280 DEG C, the flow of water vapour is 100L/ hours, and by diamond heating to 620 DEG C, constant temperature time is 10 hours.Gained molecular sieve numbering is BS-5.
Embodiment 6
BS-1 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 15g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 5：1, temperature is 80 DEG C, and the time is 2 hours, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-1, and physico-chemical property is listed in table 1.
Embodiment 7
BS-1 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 43g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 8：1, temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-2, and physico-chemical property is listed in table 1.
Embodiment 8
BS-2 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 23.5g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 10：1, temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-3, and physico-chemical property is listed in table 1.
Embodiment 9
BS-2 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 51.3g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 6：1, temperature is 75 DEG C, and the time is 1 hour, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-4, and physico-chemical property is listed in table 1.
Embodiment 10
BS-3 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 27.8g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 8：1, temperature is 95 DEG C, and the time is 3 hours, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-5, and physico-chemical property is listed in table 1.
Embodiment 11
BS-3 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 56.7g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 4：1, temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-6, and physico-chemical property is listed in table 1.
Embodiment 12
BS-4 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 33.5g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 4：1, temperature is 75 DEG C, and the time is 3 hours, after constant temperature terminates, slurries is filtered, and the filter cake water for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-7, and physico-chemical property is listed in table 1.
Embodiment 13
BS-5 molecular sieve 200g are taken, with concentration for the ammonium fluosilicate aqueous solution of 45.8g ammonium fluosilicates/100mL solution is contacted, the solid volume ratio of liquid is 12：1, temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, slurries is filtered, and the filter cake water purification for obtaining is in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the invention, and numbering is BSS-8, and physico-chemical property is listed in table 1.
Comparative example 1
Modified beta molecular sieve is prepared using method disclosed in CN1393522A, numbering is BD-1, and physico-chemical property is listed in table 1, and detailed process is as follows：
Beta-molecular sieve original powder 400g in Example 1, with 2.0M ammonium nitrate solutions, with liquid, volume ratio is 10 admittedly:1 is swapped, and is warming up to 90 ~ 95 DEG C, and constant temperature is stirred 2 hours, is then cooled to 50 ~ 60 DEG C of filterings, and wet cake carries out second exchange again, and condition is with for the first time.Through the beta-molecular sieve that ammonium salt twice is exchanged, washing reaches 5 ~ 6, is then placed in drying box to pH, 110 ~ 120 DEG C of dryings 6 hours.Dried beta-molecular sieve is rapidly heated to 250 DEG C in being put into muffle furnace, and constant temperature 2 hours then proceedes to be rapidly heated to 400 DEG C, then constant temperature 4 hours, is finally warmed up to 540 DEG C, and constant temperature 10 hours obtains the beta-molecular sieve BD-0 after the de- ammonium of high-temperature roasting.Weigh after the beta-molecular sieve BD-0 after the 400g de- ammoniums of the high-temperature roasting as obtained in the above method is crushed and add 0.4M HCl 4000mL, stirring is warming up to 90 DEG C, and constant temperature is stirred 2 hours, cold filtration washing.Through the beta-molecular sieve filtration washing of acid treatment, then in 110 ~ 120 DEG C of dryings 6 hours（Butt>80wt%）.Quantitative water purification will be uniformly sprayed on above-mentioned dry sample, be put into closed hydro-thermal process stove, be warming up to 650 DEG C, control pressure 450kPa, constant temperature and pressure is calcined 2.5 hours, and room temperature is then down to naturally, that is, obtain beta-molecular sieve BD-1.
Using the solid phase nuclear-magnetism of 500MHZ, to beta-molecular sieve BSS-1 obtained in the embodiment of the present invention 6 and obtained in comparative example 1, beta-molecular sieve BD-1 is characterized, respective27Al
MAS NMR spectras difference is as depicted in figs. 1 and 2.In Fig. 1 and Fig. 2, the non-framework aluminum of the peak correspondence hexa-coordinate near 0ppm, and the framework aluminum of the peak correspondence four-coordination near 60ppm, and peak area can regard two kinds of ratios of constructed of aluminium as.It will be seen from figure 1 that there's almost no hexa-coordinate non-framework aluminum in the aluminium spectrum of molecular sieve of the present invention, and the peak intensity of four-coordination framework aluminum is stronger, and half-peak breadth is narrower, illustrates that constructed of aluminium in molecular sieve is substantially the four-coordination aluminium structure of skeleton；Fig. 2 molecular sieves then have substantial amounts of hexa-coordinate non-framework aluminum structure, more than the 20% of aluminium content almost in molecular sieve.
Comparative example 2
Ammonium is first passed through using beta-molecular sieve in CN1166560C to exchange, then slough the method for template prepare molecular sieve, it is specific as follows：
（1）Take commercial synthesis SiO2/Al2O3Mol ratio 25.67, Na2O
Slurries 2000mL, 400g containing solid phase during the Na beta-molecular sieves of 3.75wt% after crystallization（In terms of butt）, solid-liquid volume ratio is diluted to 1 with water purification：10, ammonium nitrate is added, make to contain ammonium nitrate for 2.0M in slurries, stir, be warming up to 95 DEG C, constant temperature is stirred 2 hours, is then cooled to 60 DEG C of filterings, and wet cake carries out second exchange again, and condition is with for the first time；
（2）Through the beta-molecular sieve that ammonium salt twice is exchanged, washing reaches 6, is then placed in drying box to pH, 110 DEG C of dryings 6 hours；
（3）Dried beta-molecular sieve is put into muffle furnace and was warming up to 250 DEG C in 1 hour, constant temperature 2 hours, then proceedes to be warming up in 1 hour 400 DEG C, then constant temperature 4 hours, is finally warmed up to 540 DEG C, and constant temperature 10 hours, material all burns white, carbon residue≤0.2%；
（4）Molecular sieve 200g is taken, it is the ammonium fluosilicate aqueous solution of 23.5g ammonium fluosilicates/100mL solution to use concentration, and the solid volume ratio of liquid is 10：1, treatment temperature is 95 DEG C, and process time is 2 hours, after constant temperature terminates, slurries is filtered, and obtains filter cake in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve, and numbering is BD-2, and physico-chemical property is listed in table 1.
Comparative example 3
Beta-molecular sieve original powder is taken with embodiment 1.Above-mentioned beta-molecular sieve original powder 1000g is taken, is fitted into closed hydro-thermal process stove, using the method for temperature programming（Heating rate is 100 DEG C/h）, 600 DEG C of hydro-thermal process temperature, hydro-thermal process pressure is 0.2MPa, process time is 3 hours, then carries out acidification by raw material of molecular sieve after hydro-thermal process, and treatment conditions are molecular sieve 200g after water intaking heat treatment, concentration is used to be processed for the hydrochloric acid solution of 0.4mol/L, the solid volume ratio of liquid is 10：1, treatment temperature is 95 DEG C, and process time is 2 hours, after constant temperature terminates, slurries is filtered, and obtains filter cake in 75 DEG C, the solid volume ratio 10 of liquid：1, wash time is 40 minutes, stops washing close to after 7 with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve, and numbering is BD-3, and physico-chemical property is listed in table 1.
Comparative example 4
Beta-molecular sieve is prepared using the method for embodiment 6, unlike, BS-1 molecular sieves are replaced by the BDS-4 molecular sieves prepared using following methods, obtain beta-molecular sieve, and numbering is BD-4, and physico-chemical property is listed in table 1.
The preparation of BDS-4 molecular sieves：Beta-molecular sieve original powder is taken with embodiment 1.Above-mentioned beta-molecular sieve original powder 1000g is taken, is fitted into closed hydro-thermal process stove, using the method for temperature programming（Heating rate is 100 DEG C/h）, 550 DEG C of hydro-thermal process temperature, hydro-thermal process pressure is 0.2MPa, and process time is 6 hours, and sample number into spectrum is BDS-4.
Comparative example 5
Gas phase aluminium-eliminating and silicon-replenishing is carried out to BS-1 molecular sieves.Load BS-1 molecular sieve 200g in closed container, be passed through the silicon tetrachloride after gasification, reaction temperature is 95 DEG C, and the reaction time is 2 hours, and the amount for being passed through silicon tetrachloride is 9.8gSiCl4/ 100g molecular sieves.Sample number into spectrum is BD-5, and physico-chemical property is listed in table 1.
Comparative example 6
Using the method for embodiment 6, unlike, change ammonium fluosilicate into equal amount（Mole meter）Tetraethyl orthosilicate, sample number into spectrum is BD-6, and physico-chemical property is listed in table 1.
Comparative example 7
Method according to embodiment 6 prepares beta-molecular sieve, unlike, the beta-molecular sieve BD-0 after the beta-molecular sieve original powder de- ammonium of the high-temperature roasting as obtained in the comparative example 1 of identical weight replaces, and obtains beta-molecular sieve, and numbering is BD-7, and physico-chemical property is listed in table 1.
The beta-molecular sieve physico-chemical property of table 1
| Embodiment is numbered | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Molecular sieve is numbered | BSS-1 | BSS-2 | BSS-3 | BSS-4 | BSS-5 | BSS-6 | BSS-7 | BSS-8 |
| Silica alumina ratio | 36.5 | 85.6 | 58.4 | 78.7 | 89.6 | 118.7 | 63.8 | 88.6 |
| 634 | 645 | 597 | 603 | 576 | 589 | 612 | 648 | |
| Pore volume, mL/g | 0.44 | 0.47 | 0.46 | 0.47 | 0.48 | 0.49 | 0.46 | 0.48 |
| Relative crystallinity, % | 110 | 118 | 120 | 121 | 125 | 130 | 119 | 117 |
| Infrared acidity, mmol/g | 0.27 | 0.23 | 0.24 | 0.22 | 0.19 | 0.16 | 0.25 | 0.22 |
| Si（0Al）In silicon and framework silicon, % | 96.2 | 97.1 | 96.7 | 96.5 | 97.8 | 98.2 | 97.0 | 97.3 |
| Non-framework aluminum accounts for total aluminium, % | 1.5 | 0.6 | 1.0 | 0.9 | 0.5 | 0.4 | 0.9 | 0.6 |
| Middle strong acid acid amount accounts for total acid content, % | 87.5 | 89.7 | 88.6 | 89.6 | 91.6 | 93.5 | 88.9 | 90.0 |
| 0.08 | 0.05 | 0.06 | 0.04 | 0.03 | 0.03 | 0.05 | 0.04 | |
| Molecular sieve yield, wt% | 88.6 | 87.5 | 89.6 | 86.9 | 88.3 | 86.4 | 88.7 | 87.2 |
Continued 1
| Comparative example is numbered | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Molecular sieve is numbered | BD-1 | BD-2 | BD-3 | BD-4 | BD-5 | BD-6 | BD-7 |
| Silica alumina ratio | 59.6 | 62.1 | 35.6 | 37.2 | 33.1 | 28.6 | 25.9 |
| 550 | 563 | 564 | 559 | 478 | 562 | 513 | |
| Pore volume, mL/g | 0.37 | 0.38 | 0.39 | 0.37 | 0.36 | 0.33 | 0.31 |
| Relative crystallinity, % | 97 | - | 98 | 96 | 92 | 95 | 96 |
| Infrared acidity, mmol/g | 0.21 | 0.38 | 0.27 | 0.29 | 0.45 | 0.86 | 0.72 |
| Si（0Al）In silicon account for framework silicon, % | 65.9 | 73.9 | 76.9 | 77.6 | 33.5 | 59.6 | 78.5 |
| Non-framework aluminum accounts for total aluminium, % | 6.5 | 3.8 | 2.6 | 2.4 | 15.3 | 19.6 | 2.9 |
| Middle strong acid acid amount accounts for total acid content, % | 76.5 | 79.9 | 82.6 | 75.6 | 33.6 | 24.9 | 77.8 |
| 0.04 | 0.06 | 0.17 | 0.10 | 2.39 | 1.85 | 0.09 | |
| Molecular sieve yield, wt% | 63.2 | 73.5 | 85.6 | 86.7 | 98.8 | 86.5 | 85.4 |
Embodiment I-1
By 15.6 grams of BSS-1 molecular sieves（Butt 90wt%）, 114.3 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 94.3 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-1, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-1, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-2
By 33.3 grams of BSS-1 molecular sieves（Butt 90wt%）, 85.7 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 100.0 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-2, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-2, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-3
By 22.2 grams of BSS-5 molecular sieves（Butt 90wt%）, 71.4 grams of amorphous silica-aluminas（SiO2 content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 128.6 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-3, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-3, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-4
By 44.4 grams of BSS-5 molecular sieves（Butt 90wt%）, 142.9 grams of amorphous silica-aluminas（SiO2 content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 28.6 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-4, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-4, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-5
By 33.3 grams of BSS-2 molecular sieves（Butt 90wt%）, 385.5 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume 0.75mL/g, specific surface area 350m2/ g, butt 70wt%）, 256.9 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 399.6 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-5, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-5, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-6
By 33.3 grams of BSS-3 molecular sieves（Butt 90wt%）, 171.3 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 128.4 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 199.8 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-6, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-6, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-7
By 33.3 grams of BSS-7 molecular sieves（Butt 90wt%）, 142.7 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 42.8 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 133.2 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-7, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-7, and carrier and corresponding catalyst property are shown in Table 2.
Embodiment I-8
By 33.3 grams of BSS-8 molecular sieves（Butt 90wt%）, 122.3 grams of amorphous silica-aluminas（SiO2Content 20wt%, pore volume 0.85mL/g, specific surface area 370m2/ g, butt 70wt%）, 324.1 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area 400m2/ g, butt 70wt%）, 285.3 grams of adhesives（Butt 30wt%, nitric acid is 0.4 with the mol ratio of small porous aluminum oxide）Mixed grind in roller is put into, is added water, be rolled into paste, then extrusion, extrusion bar is calcined 4 hours in 110 DEG C of dryings 4 hours at 550 DEG C, obtains carrier ZS-8, and property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of temperature programming is calcined 4 hours, obtains catalyst HC-8, and carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -1
Method according to embodiment I-2 prepares carrier, unlike, BSS-1 molecular sieves are replaced by the beta-molecular sieve BD-2 of identical weight, obtain carrier ZDS-1, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-2 using above-mentioned carrier, catalyst HCD-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -2
Method according to embodiment I-3 prepares carrier, unlike, BSS-5 molecular sieves are replaced by the beta-molecular sieve BD-3 of identical weight, obtain carrier ZDS-2, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-3 using above-mentioned carrier, catalyst HCD-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -3
Method according to embodiment I-4 prepares carrier, unlike, BSS-5 molecular sieves are replaced by the beta-molecular sieve BD-1 of identical weight, obtain carrier ZDS-3, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-4 using above-mentioned carrier, catalyst HCD-3 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -4
Method according to embodiment I-2 prepares carrier, unlike, BSS-1 molecular sieves are replaced by the beta-molecular sieve BD-4 of identical weight, obtain carrier ZDS-4, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-2 using above-mentioned carrier, catalyst HCD-4 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -5
Method according to embodiment I-2 prepares carrier, unlike, BSS-1 molecular sieves are replaced by the beta-molecular sieve BD-5 of identical weight, obtain carrier ZDS-5, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-2 using above-mentioned carrier, catalyst HCD-5 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -6
Method according to embodiment I-2 prepares carrier, unlike, BSS-1 molecular sieves are replaced by the beta-molecular sieve BD-6 of identical weight, obtain carrier ZDS-6, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-2 using above-mentioned carrier, catalyst HCD-6 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative Example I -7
Method according to embodiment I-2 prepares carrier, unlike, BSS-1 molecular sieves are replaced by the beta-molecular sieve BD-7 of identical weight, obtain carrier ZDS-7, and property is shown in Table 2.
Catalyst is prepared according to the method for embodiment I-2 using above-mentioned carrier, catalyst HCD-7 is obtained, carrier and corresponding catalyst property are shown in Table 2.
The physico-chemical property of the catalyst carrier of table 2 and catalyst
| Embodiment is numbered | I-1 | I-2 | I-3 | I-4 | I-5 | I-6 | I-7 | I-8 |
| Carrier | ||||||||
| Numbering | ZS-1 | ZS-2 | ZS-3 | ZS-4 | ZS-5 | ZS-6 | ZS-7 | ZS-8 |
| Beta-molecular sieve, wt% | 7 | 15 | 10 | 20 | 5 | 10 | 15 | 7 |
| Amorphous silica-alumina, wt% | 40 | 30 | 25 | 50 | 45 | 40 | 50 | 20 |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 0.74 | 0.73 | 0.75 | 0.68 | 0.76 | 0.72 | 0.67 | 0.78 |
| 415 | 440 | 431 | 456 | 428 | 430 | 416 | 443 | |
| Catalyst | ||||||||
| Numbering | HC-1 | HC-2 | HC-3 | HC-4 | HC-5 | HC-6 | HC-7 | HC-8 |
| 17.5 | 21.5 | 22.9 | 27.6 | 21.6 | 23.5 | 21.8 | 27.0 | |
| NiO, wt% | 4.3 | 5.3 | 5.6 | 7.5 | 5.4 | 5.5 | 5.4 | 6.7 |
| Pore volume, mL/g | 0.58 | 0.55 | 0.52 | 0.44 | 0.53 | 0.51 | 0.38 | 0.49 |
| 329 | 334 | 308 | 299 | 311 | 315 | 301 | 300 |
The physico-chemical property of the catalyst carrier of continued 2 and catalyst
| Comparative example is numbered | I-1 | I-2 | I-3 | I-4 | I-5 | I-6 | I-7 |
| Carrier | |||||||
| Numbering | ZDS-1 | ZDS-2 | ZDS-3 | ZDS-4 | ZDS-5 | ZDS-6 | ZDS-7 |
| Beta-molecular sieve, wt% | 15 | 10 | 20 | 15 | 15 | 15 | 15 |
| Amorphous silica-alumina, wt% | 30 | 25 | 50 | 30 | 30 | 30 | 30 |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 0.68 | 0.70 | 0.57 | 0.59 | 0.65 | 0.65 | 0.61 |
| 401 | 369 | 336 | 358 | 347 | 409 | 388 | |
| Catalyst | |||||||
| Numbering | HCD-1 | HCD-2 | HCD-3 | HCD-4 | HCD-5 | HCD-6 | HCD-7 |
| 21.8 | 23.8 | 27.5 | 21.4 | 21.6 | 21.6 | 21.5 | |
| NiO, wt% | 5.5 | 6.1 | 7.4 | 5.4 | 5.5 | 5.2 | 5.3 |
| Pore volume, mL/g | 0.50 | 0.49 | 0.32 | 0.33 | 0.41 | 0.36 | 0.34 |
| 301 | 263 | 241 | 256 | 251 | 278 | 254 |
Catalytic performance test 1
Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：Reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1500, volume space velocity 0.9h during liquid-1, use vacuum distillate（VGO）Used as feedstock oil, raw material oil nature is listed in table 3.Catalyst HC-1 to HC-8 and HCD-1 to HCD-7 is evaluated under identical process conditions, the evaluation result for obtaining is listed in table 4.
The raw material oil nature of table 3
| Feedstock oil | VGO-1 | VGO-2 |
| 0.9054 | 0.9118 | |
| Boiling range/DEG C | ||
| IBP/10% | 303/362 | 316/385 |
| 30%/50% | 393/415 | 417/443 |
| 70%/90% | 445/485 | 475/520 |
| 95%/EBP | 510/554 | 543/553 |
| Condensation point, DEG C | 35 | 33 |
| Sulphur, wt% | 2.08 | 1.76 |
| Nitrogen, μ g/g | 1180 | 1236 |
| Carbon, wt% | 85.28 | 85.35 |
| Hydrogen, wt% | 12.52 | 12.77 |
| BMCI values | 44.06 | 44.40 |
The performance evaluation condition of table 4 and result
| Catalyst | HC-1 | HC-2 | HC-3 | HC-4 | HC-5 | HC-6 | HC-7 | HC-8 |
| Feedstock oil | VGO-1 | VGO-1 | VGO-1 | VGO-1 | VGO-1 | VGO-2 | VGO-2 | VGO-2 |
| 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | |
| Reaction stagnation pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1500 | 1500 | 1500 | 1500 | 1500 | 1500 | 1500 | 1500 |
| Reaction temperature, DEG C | 378 | 385 | 380 | 375 | 386 | 381 | 377 | 385 |
| Product yield and property | ||||||||
| Heavy naphtha | ||||||||
| Yield, wt% | 4.1 | 4.5 | 4.8 | 3.8 | 4.3 | 4.6 | 3.9 | 4.6 |
| Virtue is latent, wt% | 57.6 | 58.6 | 56.9 | 55.6 | 58.2 | 56.2 | 59.6 | 57.6 |
| Jet fuel | ||||||||
| Yield, wt% | 19.6 | 18.8 | 18.6 | 17.9 | 18.9 | 21.0 | 17.3 | 18.5 |
| Smoke point, mm | 25 | 26 | 26 | 25 | 27 | 26 | 26 | 27 |
| Aromatic hydrocarbons, v% | 7.5 | 7.2 | 7.2 | 8.4 | 7.1 | 6.8 | 7.2 | 6.4 |
| Diesel oil | ||||||||
| Yield, wt% | 47.6 | 48.2 | 47.9 | 47.6 | 49.6 | 46.5 | 48.6 | 47.5 |
| Condensation point, DEG C | -20 | -18 | -19 | -17 | -20 | -22 | -19 | -21 |
| Cetane number | 51.2 | 50.6 | 50.9 | 50.0 | 52.3 | 53.0 | 51.6 | 54.6 |
| Tail oil | ||||||||
| Yield, wt% | 26.1 | 25.7 | 26.3 | 28.5 | 24.4 | 25.4 | 27.8 | 25.1 |
| Condensation point, DEG C | 12 | 13 | 14 | 15 | 12 | 14 | 14 | 11 |
| BMCI values | 14.2 | 13.5 | 13.8 | 14.6 | 13.2 | 12.1 | 12.0 | 12.5 |
| Chemical hydrogen consumption, wt% | 2.04 | 2.06 | 2.05 | 1.98 | 2.09 | 2.10 | 2.01 | 2.02 |
The performance evaluation condition of continued 4 and result
| Catalyst | HCD-1 | HCD-2 | HCD-3 | HCD-4 | HCD-5 | HCD-6 | HCD-7 |
| Feedstock oil | VGO-1 | VGO-1 | VGO-1 | VGO-1 | VGO-1 | VGO-1 | VGO-1 |
| 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | |
| Reaction stagnation pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1500 | 1500 | 1500 | 1500 | 1500 | 1500 | 1500 |
| Reaction temperature, DEG C | 392 | 395 | 403 | 398 | 407 | 412 | 395 |
| Product yield and property | |||||||
| Heavy naphtha | |||||||
| Yield, wt% | 5.9 | 6.3 | 7.8 | 6.8 | 8.8 | 7.7 | 6.1 |
| Virtue is latent, wt% | 51.5 | 50.6 | 48.2 | 49.6 | 43.6 | 46.3 | 50.4 |
| Jet fuel | |||||||
| Yield, wt% | 20.6 | 21.1 | 20.5 | 18.6 | 22.6 | 21.3 | 20.5 |
| Smoke point, mm | 24 | 23 | 25 | 22 | 24 | 21 | 22 |
| Aromatic hydrocarbons, v% | 8.9 | 9.6 | 9.6 | 10.2 | 9.6 | 12.6 | 9.8 |
| Diesel oil | |||||||
| Yield, wt% | 43.8 | 42.1 | 40.2 | 39.6 | 37.5 | 38.4 | 42.9 |
| Condensation point, DEG C | -8 | -6 | -7 | -5 | -8 | -5 | -5 |
| Cetane number | 47.8 | 47.3 | 46.5 | 45.6 | 44.36 | 47.6 | 46.5 |
| Tail oil | |||||||
| Yield, wt% | 25.9 | 25.6 | 26.5 | 27.9 | 25.5 | 26.5 | 26.7 |
| Condensation point, DEG C | 22 | 20 | 25 | 23 | 25 | 21 | 25 |
| BMCI values | 15.6 | 14.3 | 17.5 | 16.8 | 18.4 | 16.3 | 15.9 |
| Chemical hydrogen consumption, wt% | 2.20 | 2.22 | 2.36 | 2.34 | 2.44 | 2.65 | 2.31 |
The catalyst of carrier preparation of the present invention can be seen that under identical process conditions by the evaluation result of table 4, diesel oil selectivity, yield and product quality are superior to reference catalyst.
Claims (23)
1. a kind of carrier of hydrocracking catalyst, comprising beta-molecular sieve, amorphous silica-alumina and aluminum oxide, the property of wherein beta-molecular sieve is as follows：SiO2/Al2O3Mol ratio 30 ~ 150, non-framework aluminum accounts for less than the 2% of total aluminium, and more than 95% of silicon atom in skeleton structure is accounted for the silicon atom of Si (OAl) structural coordinates.
2. according to the catalyst carrier described in claim 1, it is characterised in that：The SiO of beta-molecular sieve2/Al2O3Mol ratio is 40 ~ 150.
3. according to the catalyst carrier described in claim 1, it is characterised in that：In the beta-molecular sieve, non-framework aluminum accounts for less than the 1% of total aluminium, and 95% ~ 99% of silicon atom in skeleton structure is accounted for the silicon atom of Si (OAl) structural coordinates.
4. according to the catalyst carrier described in claim 3, it is characterised in that：96% ~ 99% of silicon atom in skeleton structure is accounted for the silicon atom of Si (OAl) structural coordinates.
5. according to the catalyst carrier described in claim 1, it is characterised in that：The SiO of the beta-molecular sieve2/Al2O3Mol ratio 60 ~ 120.
6. according to the catalyst carrier described in claim 1, it is characterised in that：The relative crystallinity of the beta-molecular sieve is 100% ~ 140%.
7. according to any described catalyst carrier of claim 1 ~ 6, it is characterised in that：Meleic acid the amount 0.1 ~ 0.5mmol/g, NH of the beta-molecular sieve3The acid amount of the middle strong acid that-TPD methods are measured accounts for more than the 80% of total acid content.
8. according to any described catalyst carrier of claim 1 ~ 6, it is characterised in that：Meleic acid amount 0.15 ~ 0.45 mmol/g, NH of the beta-molecular sieve3The acid amount of the middle strong acid that-TPD methods are measured accounts for the 85% ~ 95% of total acid content.
9. according to any described catalyst carrier of claim 1 ~ 6, it is characterised in that：The Na of the beta-molecular sieve2O≤0.15wt%。
10. according to the catalyst carrier described in claim 9, it is characterised in that：The Na of the beta-molecular sieve2O≤0.10wt%。
11. according to any described catalyst carrier of claim 1 ~ 6, it is characterised in that：The specific surface area of the beta-molecular sieve is 400m2/g~800m2/ g, total pore volume is 0.30mL/g ~ 0.50mL/g.
12. according to the catalyst carrier described in claim 7, it is characterised in that：The specific surface area of the beta-molecular sieve is 400m2/g~800m2/ g, total pore volume is 0.30mL/g ~ 0.5mL/g, Na2O≤0.15wt%。
13. according to the catalyst carrier described in claim 1, it is characterised in that：SiO in described amorphous silica-alumina2Weight content be 5% ~ 40%, the pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, and specific surface area is 300 ~ 500m2/g。
14. according to the catalyst carrier described in claim 1, it is characterised in that：Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of beta-molecular sieve is 3% ~ 20%, and the content of amorphous silica-alumina is 10% ~ 70%, and the content of aluminum oxide is 15% ~ 70%.
15. according to the catalyst carrier described in claim 1, it is characterised in that：Described support is as follows：Specific surface area is 300 ~ 500m2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of any described carrier of 16. claims 1 ~ 15, including：
Then beta-molecular sieve, amorphous silica-alumina, aluminum oxide mechanical mixture, shaping are dried and be calcined, catalyst carrier is made；The wherein preparation method of beta-molecular sieve, including：
（1）Beta-molecular sieve original powder is contacted with normal pressure, dynamic water vapour, the temperature of contact is 500 ~ 650 DEG C, and the time is 5 ~ 10 hours；
（2）By step（1）The product of gained is contacted with ammonium fluosilicate, is then filtered, washes and is dried, and obtains beta-molecular sieve.
17. in accordance with the method for claim 16, it is characterised in that：Step（1）In, beta-molecular sieve original powder is synthesized using hydro-thermal method by template of organic amine, its SiO2/Al2O3Mol ratio 22.5 ~ 28.5, Na2O content is 1.0wt% ~ 3.0wt%.
18. according to the method described in claim 16 or 17, it is characterised in that：Step（1）In, using temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, starts to introduce water vapour, and is continuously heating to 500 ~ 650 DEG C, is then stopped 5 ~ 10 hours at this temperature.
19. according to the method described in claim 16 or 17, it is characterised in that：Step（1）In, water vapour is by every kilogram of beta-molecular sieve original 50 ~ 100L/h of powder by beta-molecular sieve original powder.
20. according to the method described in claim 16 or 17, it is characterised in that：Step（1）Using the 100wt% steam treatments of flowing.
21. according to the method described in claim 16 or 17, it is characterised in that：Step（2）The concentration of the ammonium fluosilicate aqueous solution of use is 10g ~ 60g/100mL solution, and the ammonium fluosilicate aqueous solution is 3 with the solid volume ratio of the liquid of beta-molecular sieve：1~15：1；The condition of the contact includes 40 ~ 120 DEG C of temperature, and the time is 0.5 ~ 8.0 hour.
22. in accordance with the method for claim 16, it is characterised in that：Step（2）Described drying condition is as follows：Dried 3 ~ 6 hours under conditions of 100 ~ 120 DEG C.
23. in accordance with the method for claim 16, it is characterised in that：The drying and roasting of carrier are as follows：In 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then it is calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C.
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| CN1393287A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Macroreticular acidic composite carrier and its preparing process |
| CN1712134A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN103100427A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier containing beta molecular sieve and preparation method thereof |
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| CN1393287A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Macroreticular acidic composite carrier and its preparing process |
| CN1712134A (en) * | 2004-06-21 | 2005-12-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN103100427A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier containing beta molecular sieve and preparation method thereof |
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