CN104667971A - 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. The carrier contains a beta molecular sieve, a Y type molecular sieve and aluminum oxide, wherein the natures of the beta molecular sieve are as follows: the molar ratio of SiO2/Al2O3 is 30-150, non-framework aluminum accounts for below 2% of total aluminum, and silicon atoms coordinated by a Si(OAl) structure account for above 95% of the silicon atoms in a framework structure. The preparation method comprises the following steps: mixing the beta molecular sieve, the Y type molecular sieve and aluminum oxide and forming for preparation. In the catalyst disclosed by the invention, the beta molecular sieve with a uniform framework silica-alumina structure and the Y type molecular sieve are jointly used as a cracking component, and the prepared catalyst has the characteristics of high activity, high yield of high-quality intermediate fraction oil and capability of simultaneously co-producing high-quality hydrogenation tail oil in a hydrocracking process.
Description
Technical field
The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, particularly adopt β and Y zeolite compounding ingredients to be predominant cracking component, be applicable to carrier of hydrocracking catalyst preparing high-output qulified intermediate oil and preparation method thereof.
Background technology
In recent years, the demand of countries in the world refined products market to high-quality middle cut oil product constantly increases always, and along with developing rapidly of economy, this imbalance between supply and demand seems more outstanding.Hydrocracking technology has become with its exclusive advantage the best means that heavy oil deep processing production high-quality cleans intermediate oil.
At present, in countries in the world, the activity of oil type hydrocracking catalyst is not very high, and the condensation point of gained diesel oil is also higher, is difficult to meet refinery and transforms existing apparatus or increase treating capacity to reach the object of volume increase intermediate oil further.
The raise productivity and improve the quality key of intermediate oil of hydrocracking is exploitation and uses suitable catalyst.Although the hydrocracking catalyst containing single molecular sieve component has very high activity, its middle distillates oil selectivity is poor, and the catalyst containing composite molecular screen but shows and can improve activity and can improve again and optionally act synergistically.
Hydrocracking technology core is catalyst, and the key component playing cracking in this type of catalyst mostly is Y zeolite and beta-molecular sieve.Relative to Y zeolite, beta-molecular sieve has three-dimensional twelve-ring pore structure, but does not have the supercage structure as Y zeolite, and its main feature is two 6 ring unit bug hole structures of two 4 rings and four 5 rings, belong to cubic system, main channel diameter is at 0.56-0.75nm.Have topological structure and the stereoscopic three-dimensional duct feature of beta-molecular sieve make it in cracking reaction, have good effect to the fracture of chain hydrocarbon-selective, and there is very strong isomery performance, can be used for Low Freezing Point middle oil fraction 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 zeolite, in three cross one another pore canal system, two linear channels are mutually orthogonal and perpendicular to [001] direction, pore size is 0.57nm × 0.75nm, 3rd twelve-ring pore canal system is parallel to [001] direction, be non-linear channels, pore size is 0.56 nm × 0.65 nm; Also there is diversity in crystallization completely beta-molecular sieve framework silicon-aluminum structure, framework silicon-aluminum structure is four-coordination structure and this structure accounts for the main body of sial existence form total in molecular sieve, its basic structure is by the different Si(4Al of content), Si(3Al), Si(2Al), Si(1Al) and Si(0Al) construction unit form, and based on Si(3Al) and Si(2Al) version; The non-framework aluminum of hexa-coordinate is also there is in addition in molecular sieve; There is different changes in the sial existing way of these various structures and content, thus will produce different catalytic performances in follow-up different modifying process.
In the existing method of modifying to beta-molecular sieve (such as CN1105646A), generally first carry out ammonium to exchange de-sodium, then high-temperature roasting removing template (organic amine), then carry out dealuminzation and constant voltage hydrothermal treatment consists, the silica alumina ratio of beta-molecular sieve can be increased substantially like this.Especially high-temperature roasting is except the process of amine, at CN99113577.6, in the patents such as CN01106042.5, lay special stress on baking inphases takes off amine, so not only preparation process is complicated, and molecular sieve first will exchange sodium through ammonium salt before ammonium is burnt in segmentation, sodium ion is for the negative electrical charge (being generally framework aluminum to be formed) in balance molecule sieve skeleton frame, and the burning ammonium process (no matter being a step high-temperature process or multistep treatment of different temperature) carried out again after de-sodium will make framework of molecular sieve dealuminzation aggravate, and there is non-selectivity framework dealumination, make the skeleton structure heterogeneity of modified molecular sieve, there is very large defect, and in duct, define non-framework aluminum structure (the blocking duct of a large amount of hexa-coordinates, part shelters skeleton acid site, the imperfect cracking reaction of easy generation), and follow-up acid treatment or hydrothermal treatment consists, all continuation is destroyed further to the skeleton structure of molecular sieve, make to also exist in framework of molecular sieve structure in the different Si of ratio (X-Al) structure and molecular sieve and there is a certain amount of non-framework aluminum structure, molecular sieve is made to have varying strength acid site, show different cracking performances, to greatly affect the selective of catalyst object product.Just because of the complexity of silicon-aluminum structure in beta-molecular sieve, adopt different method of modifying to make modified framework of molecular sieve structure heterogeneity in said method, directly affect the acid strength of modified molecular screen and sour density, and then affect the performance of catalyst.
A kind of method of modifying of beta-molecular sieve is disclosed in CN101450318A.The method is exchanged sodium form beta-molecular sieve and ammonium salt, with phosphorus-containing compound solution and the solution containing transistion metal compound, dipping modification is carried out to molecular sieve again, the beta-molecular sieve obtained has higher specific area and the relative crystallinity of Geng Gao, can generate low-carbon alkene by shape slective cracking further.
CN01114175.1 discloses a kind of method of modifying of beta-molecular sieve.The method process is as follows: (1) crystallization completely beta-molecular sieve directly carries out ammonium salt exchange, (2) ammonium salt exchange after beta-molecular sieve carry out filtering, wash, dry and roasting, (3) beta-molecular sieve after roasting takes off ammonium carries out acid treatment, filtration, and the complete beta-molecular sieve of (4) acid treatment carries out pressurized thermal water process.In the method, first acid treatment is carried out to β zeolite, and then carry out hydrothermal treatment consists, adopt mineral acid treatment in acid treatment process, the skeleton structure of moieties sieve will be destroyed in this course, molecular sieve crystallinity declines, the non-skeleton structure forming bulk is stayed in molecular sieve pore passage, be difficult to be removed, affect acid distribution and the acid strength of modified molecular screen, in addition, also high-temperature water heat treatment has been carried out after acid treatment, also a certain amount of non-framework aluminum can be formed in molecular sieve, this will directly affect pore structure and the Acidity of molecular sieve, the acid distribution of molecular sieve and the change of Acidity using directly affect thus molecular sieve as the performance of the catalyst of Cracking Component, especially the character of hydrocracking diesel oil and chemical industry material is affected.The step of the method modified molecular screen is longer in addition, and in preparation process, the yield of molecules of interest sieve is lower, and the modification of multi-step makes modification cost and energy consumption greatly improve simultaneously.
Summary 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 jointly done as Cracking Component by the beta-molecular sieve of uniform framework silicon-aluminum structure and Y zeolite, and act synergistically with other component, and prepared catalyst has active height and high-output qulified midbarrel wet goods feature.
Carrier of hydrocracking catalyst of the present invention, comprises beta-molecular sieve, Y zeolite and aluminium oxide, and wherein the character of beta-molecular sieve is as follows: SiO
2/ Al
2o
3mol ratio 30 ~ 150, is preferably 40 ~ 150, more preferably 60 ~ 120, non-framework aluminum accounts for less than 2% of total aluminium, is preferably less than 1%, with Si(0Al) silicon atom of structural coordinates accounts for more than 95% of silicon atom in skeleton structure, be preferably 95% ~ 99%, more preferably 96% ~ 99%.
In the present invention, described beta-molecular sieve, its character is preferably as follows: relative crystallinity is 100% ~ 140%.
In the present invention, described beta-molecular sieve, its character is preferably as follows: meleic acid amount is 0.1 ~ 0.5mmol/g, preferably 0.15 ~ 0.45mmol/g, NH
3the acid amount of the middle strong acid that-TPD method records accounts for more than 80% of total acid content, is preferably 80% ~ 95%, more preferably 85% ~ 95%.
In the present invention, described beta-molecular sieve, its character is preferably as follows: Na
2o≤0.15wt%, is preferably Na
2o≤0.10wt%.
In the present invention, described beta-molecular sieve, its character is preferably as follows: specific area is 400m
2/ g ~ 800m
2/ g, is preferably 500 m
2/ g ~ 700m
2/ g, total pore volume is 0.3mL/g ~ 0.50mL/g.
In beta-molecular sieve of the present invention, total aluminium refers to the summation of the aluminium in molecular sieve in framework aluminum and the aluminium in non-framework aluminum.Non-framework aluminum refers in molecular sieve with the aluminium that hexa-coordinate version exists.Framework aluminum refers in molecular sieve with the aluminium that four-coordination version exists.Silicon atom (framework silicon atom) in skeleton structure, namely with Si(4Al), Si(3Al), Si(2Al), Si(1Al) and the summation of the Si(0Al) silicon atom of structural coordinates.Wherein, Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al) be the four-coordination structure (i.e. skeleton structure) of different co-ordination state from the silicon atom in silicon-oxy tetrahedron, Si(4Al) refer to the four-coordination structure that the silicon atom in silicon-oxy tetrahedron is only directly connected with 4 aluminum-oxygen tetrahedrons and Si [(OAl)
4], Si(3Al) refer to the four-coordination structure that silicon atom in silicon-oxy tetrahedron and 3 aluminum-oxygen tetrahedrons and 1 silicon-oxy tetrahedron are directly connected and Si [(OAl)
3(OSi)
1], Si(2Al) be that namely silicon atom in silicon-oxy tetrahedron refers to Si [(OAl) with the four-coordination structure that 2 aluminum-oxygen tetrahedrons and 2 silicon-oxy tetrahedrons are directly connected
2(OSi)
2], Si(1Al) refer to the four-coordination structure Si [(OAl) that the silicon atom in silicon-oxy tetrahedron is directly connected with 1 aluminum-oxygen tetrahedron and 3 silicon-oxy tetrahedrons
1(OSi)
3], Si(0Al) refer to the four-coordination structure Si [(OSi) that the silicon atom in silicon-oxy tetrahedron is only directly connected with 4 silicon-oxy tetrahedrons
4].
Described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, the content of beta-molecular sieve is 5% ~ 20%, and the content of Y zeolite is 10% ~ 40%, and the content of aluminium oxide is 40% ~ 85%.
Described Y zeolite, its character is as follows: specific area is 850m
2/ g ~ 950m
2/ g, total pore volume is 0.43mL/g ~ 0.55mL/g, SiO
2/ Al
2o
3mol ratio is 20 ~ 150, and cell parameter is 2.425 ~ 2.433nm, meleic acid amount 0.1 ~ 0.4mmol/g.This Y zeolite can adopt prior art to prepare.
Carrier of hydrocracking catalyst character of the present invention is as follows: specific area is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of carrier of hydrocracking catalyst of the present invention, comprises the steps:
By beta-molecular sieve, Y zeolite, aluminium oxide mechanical mixture, shaping, then dry and roasting, makes catalyst carrier; The wherein preparation method of beta-molecular sieve, comprising:
(1) contacted with normal pressure, dynamic water vapour by former for beta-molecular sieve powder, the temperature of contact is 500 ~ 650 DEG C, and the time is 5 ~ 10 hours;
(2) product of step (1) gained contacted with ammonium fluosilicate, then filter, wash and drying, obtain beta-molecular sieve.
The former powder of step (1) beta-molecular sieve is that template adopts water heat transfer, its SiO with organic amine
2/ Al
2o
3mol ratio 22.5 ~ 28.5, Na
2o content is 1.0wt% ~ 3.0wt%.
The former powder of step (1) beta-molecular sieve is in normal pressure, dynamic water vapour condition process, and the general water vapour of flowing that adopts carries out, and adopt 100wt% water vapour, water vapour passes through molecular screen primary powder by every kilogram of former powder 50 ~ 100L/h of beta-molecular sieve.
In step (2), contacted by the product of step (1) gained, its condition with ammonium fluosilicate: temperature 40 ~ 120 DEG C, be preferably 70 ~ 100 DEG C, the time is 0.5 ~ 8.0 hour, preferably 1.0 ~ 3.0 hours.Described washing conditions: the general deionized water that adopts is washed, until cleaning solution pH value is close to neutrality.Described drying condition is as follows: drying 3 ~ 6 hours under the condition of 100 ~ 120 DEG C.
In catalyst support preparation method of the present invention, the drying of carrier and roasting can adopt conventional condition, are generally 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 hours.
The beta-molecular sieve that catalyst carrier of the present invention adopts has the features such as uniform framework silicon-aluminum structure, acidity is suitable, pore structure is reasonable, suitable to Cracking Component, make catalyst have higher catalytic activity and isomerism ability, be suitable for the midbarrel oil product of production high-quality and high-quality industrial chemicals product.
First the inventive method adopts normal pressure, Dynamic Hydrothermal process molecular screen primary powder, do not need through preprocessing process such as ammonium exchanges, molecular sieve can be realized take off ammonium (Template removal) and selective reduction framework aluminum activation energy under the effect of dynamic high temperature water vapour, and avoid framework of molecular sieve structural damage, and keep the homogeneity of framework of molecular sieve structure, match with follow-up ammonium hexafluorosilicate modifying process, effectively low-energy framework aluminum evenly can be deviate from, and silicon atom is supplemented on skeleton, make the skeleton structure of molecular sieve more homogeneous and stable, simultaneously, sodium ion in molecular sieve is also together taken out of, sodium content in molecular sieve can be taken off below 0.15wt%, thus overcome in prior art carry out multistep ammonium exchange (washing sodium) and energy consumption high, pollute the shortcomings such as large.The inventive method can further unimpeded pore passage structure by ammonium hexafluorosilicate, the non-framework aluminum of generation can be deviate from from molecular sieve pore passage, the object reaching non-framework aluminum He make molecular sieve pore passage more unobstructed.The present invention by optimizing method of modifying, make modified molecular sieve have uniform framework silicon-aluminum structure, pore structure rationally, acid centre intensity and sour Density Distribution more even, be conducive to provide uniform cracking center, improve the object product selectivity of catalyst.
Beta-molecular sieve of the present invention and Y zeolite are jointly as cracking center, both its respective performance characteristics had been given full play to, the concerted catalysis effect that two kinds of molecular sieves produce can be made again, namely beta-molecular sieve has good isomerization to the long side chain on alkane or aromatic hydrocarbons, effectively can reduce the condensation point of product, Y zeolite has very high selectivity of ring-opening to aromatic hydrocarbons simultaneously, improves the product property of object product.Hydrocracking catalyst prepared by carrier of the present invention has active high, can high-output qulified midbarrel oil product (boat coal+diesel oil), can hold concurrently simultaneously and produce the hydrogenation tail oil of high-quality.
Accompanying drawing explanation
Fig. 1 is: beta-molecular sieve of the present invention in embodiment 6
27al MASNMR spectrogram, wherein abscissa is ppm;
Fig. 2 is: contrast molecular sieve in comparative example 1
27al MASNMR spectrogram, wherein abscissa is ppm.
Detailed description of the invention
In carrier of hydrocracking catalyst of the present invention, aluminium oxide can adopt aluminium oxide used in conventional hydrocracking catalyst, as macroporous aluminium oxide and ∕ or little porous aluminum oxide.Pore volume 0.7 ~ the 1.0mL/g of macroporous aluminium oxide used, specific area 200 ~ 500m
2/ g.The pore volume of little porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific area is 200 ~ 400m
2/ g.
The such as peptization acid of conventional shaping assistant can also be added, extrusion aid etc. in catalyst support preparation process of the present invention.
The preparation method of the beta-molecular sieve that carrier of hydrocracking catalyst of the present invention is used, specifically comprises the steps:
(1) contacted with normal pressure, dynamic water vapour by former for beta-molecular sieve powder, the temperature of contact is 500 ~ 650 DEG C, and the time is 5 ~ 10 hours;
(2) product of step (1) gained contacted with ammonium fluosilicate, then filter, wash and drying, obtain beta-molecular sieve.
In step (1), the mode that the former powder of beta-molecular sieve contacts with normal pressure, dynamic water vapour, is preferably placed in container by former for beta-molecular sieve powder, then introduces water vapour from one end of container, discharged by the other end from container after the former powder of beta-molecular sieve.In order to make molecular sieve process evenly, preferably molecular sieve is placed in rotary container such as tube furnace, the other end of water vapour again from container after passing into molecular sieve from one end of container is gone out.Pressure in container keeps atmospheric pressure state, and Contact Temperature remains on 500 ~ 650 DEG C, and the processing time is 5 ~ 10 hours;
Under preferable case, step (1) adopts temperature programming, and heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, preferred 250 ~ 400 DEG C time further, start to introduce water vapour, and continue to be warming up to 500 ~ 650 DEG C, then stop 5 ~ 10 hours at this temperature.
Under preferable case, the former powder of step (1) beta-molecular sieve adopts conventional water heat transfer, usual employing organic amine is template, conventional organic amine template can adopt in tetraethyl ammonium hydroxide, TMAH, tetraethylammonium bromide etc. one or more.Usually containing template in the former powder of beta-molecular sieve, and the weight content of template is generally 10% ~ 15%.The character of the former powder of beta-molecular sieve is as follows: SiO
2/ Al
2o
3mol ratio 22.5 ~ 28.5, Na
2o content is 1.0wt% ~ 3.0wt%.In the former powder of beta-molecular sieve, template content can adopt differential scanning calorimetry (DSC)-DTG (TG) to obtain, wherein DTG adopts German Netzsch company STA449C-QMS403C type instrument, 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 is about 10mg, and the loss of weight gauge getting the former powder of beta-molecular sieve between 150 DEG C ~ 500 DEG C is the amount of template.
The former powder of step (1) beta-molecular sieve is in normal pressure, dynamic water vapour condition process, and adopt 100wt% water vapour, water vapour passes through molecular screen primary powder by every kilogram of former powder 50 ~ 100L/h of beta-molecular sieve.
The product of step (1) gained contacts with ammonium fluosilicate by step (2).The condition of described contact comprises: temperature is 40 ~ 120 DEG C, and be preferably 70 ~ 100 DEG C, the time is 0.5 ~ 8.0 hour, is preferably 1.0 ~ 3.0 hours.
Under preferable case, step (2) adopts the ammonium fluosilicate aqueous solution to contact with the beta-molecular sieve of step (1) gained, the concentration of the ammonium fluosilicate aqueous solution is 10g ~ 60g/100mL solution, and the liquid-solid volume ratio of the ammonium fluosilicate aqueous solution and beta-molecular sieve is 3:1 ~ 15:1, is preferably 4:1 ~ 10:1.
Slurries after step (2) being contacted directly filter, and the filter cake after filtration is again through washing for several times.Wherein said washing generally adopts deionized water to wash, until cleaning solution pH value is close to neutrality.Wash temperature can be 50 ~ 100 DEG C, and be preferably 60 ~ 90 DEG C, liquid-solid volume ratio is generally 5:1 ~ 15:1, and wash time is 0.5 ~ 1.0 hour, with cleaning solution pH value close to till neutrality.Described drying preferably under the condition of 100 ~ 120 DEG C dry 3 ~ 6 hours.
The yield of the beta-molecular sieve of the inventive method modification is at more than 85wt%.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiments.In the present invention, wt% is mass fraction.
Specific area described in the present invention adopts low temperature liquid nitrogen determination of adsorption method according to ASTM D3663-2003 standard.
Pore volume described in the present invention adopts low temperature liquid nitrogen determination of adsorption method according to ASTM D4222-2003 standard.
In the present invention, NH
3-TPD method is the method for a kind of conventional measurement molecular sieve acid amount, and the instrument of employing is Mike instrument company Auto-Chem II 2920 type chemical adsorption instrument.Adopt ammonia as adsorption desorption medium, helium (purity is 99.99v%), as carrier gas, adopts temperature programmed desorption and chromatography to obtain the acid amount in different desorption temperature district and weak acid amount, middle strong acid amount and strong acid amount and total acid content.Specific operation process is as follows: get 20 ~ 40 order sieve sample 0.1g, and under helium exists (helium flow velocity is 30mL/min), be warming up to 500 DEG C, constant temperature 1 hour, is then down to 150 DEG C, constant temperature 5 minutes.Afterwards, pass into ammonia until molecular sieve adsorption is saturated, switch to helium and purge continuously (helium flow velocity is 30mL/min), programming rate is 10 DEG C/min, heat up 250 DEG C, constant temperature 1 hour, continues to be warming up to 400 DEG C afterwards again, constant temperature 1 hour, then continue to be warming up to 500 DEG C, constant temperature 1 hour.In ammonia desorption process, by chromatograph record ammonia desorption spectrogram.In the ammonia desorption spectrogram of gained, be divided into the acid amount of three humidity provinces that is 150 DEG C ~ 250 DEG C, 250 DEG C ~ 400 DEG C, 400 DEG C ~ 500 DEG C corresponding weak acid of difference, middle strong acid and strong acid by desorption temperature, the acid amount sum of weak acid, middle strong acid and strong acid is total acid content.Suan Liang unit is: mmol/g, i.e. the ammonia amount of every gram molecule sieve absorption.
Meleic acid amount of the present invention take pyridine as adsorbent, and adopt infrared spectroscopic determination, instrument is America NI COLET company Nicolet 6700 Fourier infrared spectrograph, and its process is as follows:
Get levigate (granularity is less than 200 orders) sample 20mg and be pressed into the thin slice that diameter is 20mm, be contained on the specimen holder of absorption cell, get 200mg sample (sheet) load the hanging in cup of quartz spring lower end (before adding sample, record its length,
x 1, mm), absorption cell and adsorption tube are connected, start purification of finding time, vacuum reaches 4 × 10
-2during Pa, be warming up to 500 DEG C keep 1h, with remove sample adsorption thing (now, be designated as sample purification rear spring length,
x 2, mm).Then be down to room temperature, Adsorption of Pyridine to saturated, then is warmed up to 160 DEG C, balances 1 hour, the pyridine of desorption physical absorption (now, be designated as Adsorption of Pyridine rear spring length,
x 3, mm), utilize pyridine weight adsorption to try to achieve total acid content, and the infrared spectrogram of gained under recording above-mentioned condition, the bands of a spectrum 1545cm that wherein B acid is corresponding
-1, the bands of a spectrum 1455cm that L acid is corresponding
-1, calculate the B acid amount ratio measured sour with L according to the peak area ratio of each bands of a spectrum, thus, obtain total acid content, B acid amount and L acid amount;
Wherein total acid content adopts pyridine weight adsorption to calculate, specific as follows:
Hooke's law (Hooke's law) (spring elongates length and stressed relation): f=k △ x
When spring is vertically placed: m=k △ x
Wherein, m is sample quality, gram; △ x is spring elongates length, mm; K is the spring coefficient of stiffiness.
total acid
c(unit: mM/gram):
Note: 79.1 is the molal weight of pyridine, unit is gram/mol.
In the present invention, relative crystallinity (relative crystallinity) adopts XRD method to measure, and instrument is Rigaku Dmax-2500 X-ray diffractometer, adopts Cuk
αradiation, the filtering of graphite monocrystalline, operation tube voltage 35KV, tube current 40mA, sweep speed (2 θ) is 2 °/min, and sweep limits is 4 °-35 °.Standard specimen is the former powder of beta-molecular sieve that the embodiment of the present invention 1 uses.
In the present invention, silica alumina ratio adopts chemical method; Sodium content adopts plasma emission spectrometry.
In the present invention, nuclear magnetic resonance spectroscopy (NMR method) is adopted to obtain
27al MAS NMR spectrogram, thus obtain the ratio of framework aluminum and non-framework aluminum, in Al atom.Nuclear magnetic resonance spectroscopy (NMR method) is adopted to obtain
29si MAS NMR spectrogram, thus obtain silicon atom with different co-ordination state (Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al)) ratio that exists of form, in Si atom.Nuclear magnetic resonance spectroscopy (NMR method) adopts Bruker AVANCE III 500 type nuclear magnetic resonance spectrometer, and wherein software adopts Topspin 2.0.In survey
29during Si MAS NMR spectrogram, accepted standard material is tetramethylsilane (TMS), and resonant frequency is 99MHz, experiment condition: 4-6 microsecond pulse width, 60-120 relaxation delay second.In survey
27during Al MAS NMR spectrogram, accepted standard material is alchlor, and resonant frequency is 133MHz, experiment condition: 4-6 microsecond pulse width, 60-120 relaxation delay second.Gained
29in Si MAS NMR spectrogram, Si(4Al) corresponding chemical shift is-81 ~-96ppm, Si(3Al) corresponding chemical shift be-96 ~-100ppm, Si(2Al) corresponding chemical shift be-100 ~-106ppm, Si(1Al) chemical shift of correspondence is-106 ~-109ppm and Si(0Al) chemical shift of correspondence is-109 ~-115ppm).Gained
27in Al MAS NMR spectrogram, the chemical shift that framework aluminum is corresponding is 40 ~ 65ppm, and the chemical shift that non-framework aluminum is corresponding is-10 ~ 10ppm.
Embodiment 1
Get the former powder of beta-molecular sieve (be that template adopts water heat transfer with tetraethyl ammonium hydroxide, in the former powder of beta-molecular sieve, the weight content of template is about 11.8%, and branch company provides by Sinopec catalyst Fushun), its chemical SiO
2/ Al
2o
3mol ratio is 25.5, Na
2o content is 2.45wt%, in its skeleton structure, passes through
29si MAS NMR spectrogram, the distribution obtaining the silicon atom that different co-ordination state form exists is as follows: Si(4Al) be 7.6%, Si(3Al) be 30.6%, Si(2Al) be 32.3%, Si(1Al) be 21.0%, Si(0Al) be 8.5%.Get the former powder 1000g of above-mentioned beta-molecular sieve, load in tube furnace, adopt the method (heating rate is 100 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 300 DEG C, the flow of water vapour is 50L/ hour, by diamond heating to 550 DEG C, constant temperature time is 6 hours.Gained molecular sieve is numbered BS-1.
Embodiment 2
Get the former powder of beta-molecular sieve with embodiment 1.Get above-mentioned molecular sieve 1000g, load in tube furnace, adopt the method (heating rate is 100 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 300 DEG C, the flow of water vapour is 70L/ hour, by diamond heating to 600 DEG C, constant temperature time is 8 hours.Gained molecular sieve is numbered BS-2.
Embodiment 3
Get the former powder of beta-molecular sieve with embodiment 1.Get above-mentioned molecular sieve 1000g, load in tube furnace, adopt the method (heating rate is 100 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 300 DEG C, the flow of water vapour is 70L/ hour, by diamond heating to 650 DEG C, constant temperature time is 10 hours.Gained molecular sieve is numbered BS-3.
Embodiment 4
Get the former powder of beta-molecular sieve (be that template adopts water heat transfer with tetraethyl ammonium hydroxide, in the former powder of beta-molecular sieve, the weight content of template is about 10.6%, and branch company provides by Sinopec catalyst Fushun), its chemical SiO
2/ Al
2o
3mol ratio is 22.5, Na
2o content is 2.35wt%, in its skeleton structure, passes through
29si MAS NMR spectrogram, the distribution obtaining the silicon atom that different co-ordination state form exists is as follows: Si(4Al) be 7.7%, Si(3Al) be 31.5%, Si(2Al) be 30.9%, Si(1Al) be 21.9%, Si(0Al) be 8.0%.Get the former powder 1000g of above-mentioned beta-molecular sieve, load in tube furnace, adopt the method (heating rate is 80 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 400 DEG C, the flow of water vapour is 80L/ hour, by diamond heating to 600 DEG C, constant temperature time is 5 hours.Gained molecular sieve is numbered BS-4.
Embodiment 5
Get the former powder of beta-molecular sieve (be that template adopts water heat transfer with tetraethyl ammonium hydroxide, in the former powder of beta-molecular sieve, the weight content of template is about 13.2%, and branch company provides by Sinopec catalyst Fushun), its chemical SiO
2/ Al
2o
3mol ratio is 28.5, Na
2o content is 2.75wt%, in its skeleton structure, passes through
29si MAS NMR spectrogram, the distribution obtaining the silicon atom that different co-ordination state form exists is as follows: Si(4Al) be 8.8%, Si(3Al) be 28.7%, Si(2Al) be 31.3%, Si(1Al) be 23.5%, Si(0Al) be 7.7%.Get the former powder 1000g of above-mentioned beta-molecular sieve, load in tube furnace, adopt the method (heating rate is 100 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 280 DEG C, the flow of water vapour is 100L/ hour, by diamond heating to 620 DEG C, constant temperature time is 10 hours.Gained molecular sieve is numbered BS-5.
Embodiment 6
Get BS-1 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 15g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 5:1, and temperature is 80 DEG C, and the time is 2 hours, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-1, physico-chemical property lists in table 1.
Embodiment 7
Get BS-1 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 43g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 8:1, and temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-2, physico-chemical property lists in table 1.
Embodiment 8
Get BS-2 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 23.5g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 10:1, and temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-3, physico-chemical property lists in table 1.
Embodiment 9
Get BS-2 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 51.3g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 6:1, and temperature is 75 DEG C, and the time is 1 hour, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-4, physico-chemical property lists in table 1.
Embodiment 10
Get BS-3 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 27.8g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 8:1, and temperature is 95 DEG C, and the time is 3 hours, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-5, physico-chemical property lists in table 1.
Embodiment 11
Get BS-3 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 56.7g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 4:1, and temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-6, physico-chemical property lists in table 1.
Embodiment 12
Get BS-4 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 33.5g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 4:1, and temperature is 75 DEG C, and the time is 3 hours, after constant temperature terminates, by slurries filter, the filter cake water obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-7, physico-chemical property lists in table 1.
Embodiment 13
Get BS-5 molecular sieve 200g, the ammonium fluosilicate aqueous solution being 45.8g ammonium fluosilicate/100mL solution with concentration contacts, liquid-solid volume ratio is 12:1, and temperature is 95 DEG C, and the time is 2 hours, after constant temperature terminates, by slurries filter, the filter cake water purification obtained at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve of the present invention, be numbered BSS-8, physico-chemical property lists in table 1.
Comparative example 1
Adopt method disclosed in CN1393522A to prepare modified beta molecular sieve, be numbered BD-1, physico-chemical property lists in table 1, and detailed process is as follows:
The former powder 400g of beta-molecular sieve in Example 1, exchanges for 10:1 with liquid-solid volume ratio with 2.0M ammonium nitrate solution, is warming up to 90 ~ 95 DEG C, constant temperature stirs 2 hours, then be cooled to 50 ~ 60 DEG C of filtrations, wet cake carries out second time again and exchanges, and condition is with first time.Through the beta-molecular sieve that twice ammonium salt exchanges, wash and reach 5 ~ 6 to pH, then put into drying box, 110 ~ 120 DEG C of dryings 6 hours.Dried beta-molecular sieve is put into muffle furnace and is rapidly heated to 250 DEG C, and then constant temperature 2 hours continue to be rapidly heated to 400 DEG C, then constant temperature 4 hours, is finally warmed up to 540 DEG C, constant temperature 10 hours, obtain high-temperature roasting take off ammonium after beta-molecular sieve BD-0.The high-temperature roasting that weighing 400g is obtained by said method takes off after the beta-molecular sieve BD-0 after ammonium pulverizes and adds 0.4M HCl 4000mL, and stir and be warming up to 90 DEG C, constant temperature stirs 2 hours, and cold filtration washs.Through acid-treated beta-molecular sieve filtration washing, then at 110 ~ 120 DEG C of dryings 6 hours (butt >80wt%).Evenly spray quantitative water purification by the sample of above-mentioned drying, put into airtight hydrothermal treatment consists stove, be warming up to 650 DEG C, controlled pressure 450kPa, constant temperature and pressure roasting 2.5 hours, is then down to room temperature naturally, namely obtains beta-molecular sieve BD-1.
The solid phase nuclear-magnetism of 500MHZ is adopted to characterize the obtained beta-molecular sieve BSS-1 of the embodiment of the present invention 6 and obtained beta-molecular sieve BD-1 of comparative example 1, respective
27al MAS NMR spectrogram respectively as depicted in figs. 1 and 2.In Fig. 1 and Fig. 2, the non-framework aluminum of the corresponding hexa-coordinate in peak near 0ppm, and the framework aluminum of the corresponding four-coordination in peak near 60ppm, and peak area can regard the ratio of two kinds of constructed of aluminiums as.As can be seen from Figure 1, there is hexa-coordinate non-framework aluminum hardly in the aluminium spectrum of molecular sieve of the present invention, and the peak intensity of four-coordination framework aluminum is comparatively strong, half-peak breadth is narrower, illustrates that in molecular sieve, constructed of aluminium is substantially all the four-coordination constructed of aluminium of skeleton; Fig. 2 molecular sieve then also exists a large amount of hexa-coordinate non-framework aluminum structures, almost reaches more than 20% of aluminium content in molecular sieve.
Comparative example 2
Adopt beta-molecular sieve in CN1166560C first to exchange through ammonium, then the method for sloughing template prepare molecular sieve, specific as follows:
(1) commercial synthesis SiO is got
2/ Al
2o
3mol ratio 25.67, Na
2slurries 2000mL in the Na beta-molecular sieve process of O 3.75wt% after crystallization, containing solid phase 400g(in butt), with water purification, solid-liquid volume ratio is diluted to 1:10, add ammonium nitrate, making to contain ammonium nitrate in slurries is 2.0M, stirs, is warming up to 95 DEG C, constant temperature stirs 2 hours, then be cooled to 60 DEG C of filtrations, wet cake carries out second time again and exchanges, and condition is with first time;
(2) through the beta-molecular sieve that twice ammonium salt exchanges, wash and reach 6 to pH, then put into drying box, 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 at 1 hour, constant temperature 2 hours, then continues to be warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, and be finally warmed up to 540 DEG C, constant temperature 10 hours, material all burns white, carbon residue≤0.2%;
(4) molecular sieve 200g is got, employing concentration is the ammonium fluosilicate aqueous solution of 23.5g ammonium fluosilicate/100mL solution, liquid-solid volume ratio is 10:1, and treatment temperature is 95 DEG C, and the processing time is 2 hours, after constant temperature terminates, slurries are filtered, obtains filter cake at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, stops washing with the pH value of cleaning solution after 7.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve, be numbered BD-2, physico-chemical property lists in table 1.
Comparative example 3
Get the former powder of beta-molecular sieve with embodiment 1.Get the former powder 1000g of above-mentioned beta-molecular sieve, load in airtight hydrothermal treatment consists stove, adopt the method (heating rate is 100 DEG C/h) of temperature programming, hydrothermal treatment consists temperature 600 DEG C, hydrothermal treatment consists pressure is 0.2MPa, processing time is 3 hours, again with molecular sieve after hydrothermal treatment consists for raw material carries out acidification, treatment conditions are molecular sieve 200g after water intaking heat treatment, employing concentration is the hydrochloric acid solution process of 0.4mol/L, liquid-solid volume ratio is 10:1, treatment temperature is 95 DEG C, processing time is 2 hours, after constant temperature terminates, slurries are filtered, obtain filter cake at 75 DEG C, liquid-solid volume ratio 10:1, wash time is 40 minutes, after 7, washing is stopped with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve, be numbered BD-3, physico-chemical property lists in table 1.
Comparative example 4
The method of embodiment 6 is adopted to prepare beta-molecular sieve, unlike, BS-1 molecular sieve is replaced by the BDS-4 molecular sieve adopting following method to prepare, and obtain beta-molecular sieve, be numbered BD-4, physico-chemical property lists in table 1.
The preparation of BDS-4 molecular sieve: get the former powder of beta-molecular sieve with embodiment 1.Get the former powder 1000g of above-mentioned beta-molecular sieve, load in airtight hydrothermal treatment consists stove, adopt the method (heating rate is 100 DEG C/h) of temperature programming, hydrothermal treatment consists temperature 550 DEG C, hydrothermal treatment consists pressure is 0.2MPa, and the processing 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 sieve.In closed container, load BS-1 molecular sieve 200g, pass into the silicon tetrachloride after gasification, reaction temperature is 95 DEG C, and the reaction time is 2 hours, and the amount passing into silicon tetrachloride is 9.8gSiCl
4/ 100g molecular sieve.Sample number into spectrum is BD-5, and physico-chemical property lists in table 1.
Comparative example 6
Adopt the method for embodiment 6, unlike, ammonium fluosilicate is changed into the ethyl orthosilicate of identical amount (mole meter), sample number into spectrum is BD-6, and physico-chemical property lists in table 1.
Comparative example 7
Beta-molecular sieve is prepared according to the method for embodiment 6, unlike, the former powder of beta-molecular sieve takes off the beta-molecular sieve BD-0 after ammonium by the high-temperature roasting that the comparative example 1 of identical weight is obtained and replaces, and obtain beta-molecular sieve, be numbered BD-7, physico-chemical property lists in table 1.
Table 1 beta-molecular sieve physico-chemical property
| 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 |
| Specific area, m 2/g | 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) silicon in 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 |
| Na 2O，wt% | 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 |
| Specific area, m 2/g | 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) silicon in accounts 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 |
| Na 2O，wt% | 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 |
Example II-1
By 22.22 grams of BSS-1 molecular sieves (butt 90wt%), 44.44 grams of Y zeolite (SiO
2/ Al
2o
3=50, lattice constant 2.431nm, pore volume 0.45mL/g, specific area 900m
2/ g, butt 90wt%), 157.1 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 100 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-1, and carrier and corresponding catalyst character are in table 2.
Example II-2
By 33.33 grams of BSS-1 molecular sieves (butt 90wt%), 44.44 grams of Y zeolite (SiO
2/ Al
2o
3=53.5, lattice constant 2.432nm, pore volume 0.49mL/g, specific area 878m
2/ g, butt 90wt%), 142.86 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 100 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-2, and carrier and corresponding catalyst character are in table 2.
Example II-3
By 11.11 grams of BSS-3 molecular sieves (butt 90wt%), 66.67 grams of Y zeolite (SiO
2/ Al
2o
3=91, lattice constant 2.4329nm, pore volume 0.52mLg, specific area 943m
2/ g, butt 90wt%), 142.86 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 100 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-3, and carrier and corresponding catalyst character are in table 2.
Example II-4
By 44.44 grams of BSS-3 molecular sieves (butt 90wt%), 55.56 grams of Y zeolite (SiO
2/ Al
2o
3=37, lattice constant 2.433nm, pore volume 0.45mL/g, specific area 887m
2/ g, butt 90wt%), 88.89 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 100 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-4.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-4, and carrier and corresponding catalyst character are in table 2.
Example II-5
By 22.22 grams of BSS-5 molecular sieves (butt 90wt%), 44.3 grams of Y zeolite (SiO
2/ Al
2o
3=91, lattice constant 2.4329nm, pore volume 0.52mL/g, specific area 943m
2/ g, butt 90wt%), 66.5 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 88.7 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-5.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-5, and carrier and corresponding catalyst character are in table 2.
Example II-6
By 22.22 grams of BSS-7 molecular sieves (butt 90wt%), 155.5 grams of Y zeolite (SiO
2/ Al
2o
3=91, lattice constant 2.4329nm, pore volume 0.52mL/g, specific area 943m
2/ g, butt 90wt%), 177.8 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 266.7 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-6.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-6, and carrier and corresponding catalyst character are in table 2.
Example II-7
By 33.33 grams of BSS-8 molecular sieves (butt 90wt%), 33.33 grams of Y zeolite (SiO
2/ Al
2o
3=37, lattice constant 2.433nm, pore volume 0.45mL/g, specific area 887m
2/ g, butt 90wt%), 142.90 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier S-7.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-7, and carrier and corresponding catalyst character are in table 2.
Comparative Example I I-1
By 33.33 grams of BD-1 molecular sieves (butt 90wt%), 44.44 grams of Y zeolite (SiO
2/ Al
2o
3=50, lattice constant 2.431nm, pore volume 0.45mL/g, specific area 900m
2/ g, butt 90wt%), 128.6 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier DS-1.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FCD-1, and carrier and corresponding catalyst character are in table 2.
Comparative Example I I-2
By 11.11 grams of BD-1 molecular sieves (butt 90wt%), 66.67 grams of Y zeolite (SiO
2/ Al
2o
3=53.5, lattice constant 2.432nm, pore volume 0.49mL/g, specific area 878m
2/ g, butt 90wt%), 128.6 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier DS-2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FCD-2, and carrier and corresponding catalyst character are in table 2.
Comparative Example I I-3
By 33.33 grams of BD-3 molecular sieves (butt 90wt%), 44.44 grams of Y zeolite (SiO
2/ Al
2o
3=91, lattice constant 2.4329nm, pore volume 0.52mL/g, specific area 943m
2/ g, butt 90wt%), 128.6 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier DS-3.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FDC-3, and carrier and corresponding catalyst character are in table 2.
Comparative Example I I-4
Carrier is prepared according to the method for example II-4, unlike, BSS-3 molecular sieve is replaced by the beta-molecular sieve BD-2 of identical weight, and obtain carrier DS-4, character is in table 2.
Use above-mentioned carrier according to the method Kaolinite Preparation of Catalyst of example II-4, obtain catalyst FCD-4, carrier and corresponding catalyst character are in table 2.
Comparative Example I I-5
Carrier is prepared according to the method for example II-2, unlike, BSS-1 molecular sieve is replaced by the beta-molecular sieve BD-4 of identical weight, and obtain carrier DS-5, character is in table 2.
Use above-mentioned carrier according to the method Kaolinite Preparation of Catalyst of example II-2, obtain catalyst FCD-5, carrier and corresponding catalyst character are in table 2.
Comparative Example I I-6
Carrier is prepared according to the method for example II-2, unlike, BSS-1 molecular sieve is replaced by the beta-molecular sieve BD-5 of identical weight, and obtain carrier DS-6, character is in table 2.
Use above-mentioned carrier according to the method Kaolinite Preparation of Catalyst of example II-2, obtain catalyst FCD-6, carrier and corresponding catalyst character are in table 2.
Comparative Example I I-7
Carrier is prepared according to the method for example II-2, unlike, BSS-1 molecular sieve is replaced by the beta-molecular sieve BD-6 of identical weight, and obtain carrier DS-7, character is in table 2.
Use above-mentioned carrier according to the method Kaolinite Preparation of Catalyst of example II-2, obtain catalyst FCD-7, carrier and corresponding catalyst character are in table 2.
Comparative Example I I-8
Carrier is prepared according to the method for example II-2, unlike, BSS-1 molecular sieve is replaced by the beta-molecular sieve BD-7 of identical weight, and obtain carrier DS-8, character is in table 2.
Use above-mentioned carrier according to the method Kaolinite Preparation of Catalyst of example II-2, obtain catalyst FCD-8, carrier and corresponding catalyst character are in table 2.
The physico-chemical property of table 2 catalyst carrier and catalyst
| Embodiment is numbered | II-1 | II-2 | II-3 | II-4 | II-5 | II-6 | II-7 |
| Carrier | |||||||
| Numbering | S-1 | S-2 | S-3 | S-4 | S-5 | S-6 | S-7 |
| Beta-molecular sieve, wt% | 10 | 15 | 5 | 20 | 15 | 5 | 15 |
| Y zeolite, wt% | 20 | 20 | 30 | 25 | 30 | 35 | 15 |
| Aluminium oxide | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 435 | 452 | 463 | 489 | 496 | 486 | 443 |
| Specific area, m 2/g | 0.68 | 0.65 | 0.66 | 0.67 | 0.65 | 0.64 | 0.69 |
| Catalyst | |||||||
| Numbering | FC-1 | FC-2 | FC-3 | FC-4 | FC-5 | FC-6 | FC-7 |
| WO 3，wt% | 22.36 | 21.63 | 22.06 | 22.18 | 24.36 | 26.78 | 22.36 |
| NiO，wt% | 5.4 | 5.5 | 5.3 | 5.5 | 5.9 | 6.3 | 5.2 |
| Specific area, m 2/g | 330 | 327 | 332 | 349 | 365 | 357 | 352 |
| Pore volume, mL/g | 0.47 | 0.46 | 0.45 | 0.48 | 0.45 | 0.47 | 0.49 |
The physico-chemical property of continued 2 catalyst carrier and catalyst
| Comparative example is numbered | II-1 | II-2 | II-3 | II-4 | II-5 | II-6 | II-7 | II-8 |
| Carrier | ||||||||
| Numbering | DS-1 | DS-2 | DS-3 | DS-4 | DS-5 | DS-6 | DS-7 | DS-8 |
| Beta-molecular sieve, wt% | 15 | 5 | 15 | 20 | 15 | 15 | 15 | 15 |
| Y zeolite, wt% | 20 | 30 | 20 | 25 | 20 | 20 | 20 | 20 |
| Aluminium oxide | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Pore volume, mL/g | 0.65 | 0.57 | 0.58 | 0.54 | 0.61 | 0.54 | 0.51 | 0.57 |
| Specific area, m 2/g | 415 | 424 | 301 | 399 | 356 | 332 | 306 | 396 |
| Catalyst | ||||||||
| Numbering | FCD-1 | FCD-2 | FCD-3 | FCD-4 | FCD-5 | FCD-6 | FCD-7 | FCD-8 |
| WO 3，wt% | 22.23 | 21.88 | 21.85 | 21.56 | 21.95 | 21.76 | 21.69 | 21.63 |
| NiO，wt% | 5.4 | 5.3 | 5.2 | 5.4 | 5.4 | 5.3 | 5.5 | 5.5 |
| Specific area, m 2/g | 289 | 273 | 233 | 256 | 231 | 216 | 234 | 241 |
| Pore volume, mL/g | 0.42 | 0.37 | 0.36 | 0.32 | 0.34 | 0.29 | 0.31 | 0.32 |
Catalytic performance test 2
Fixed bed hydrogenation experimental rig is evaluated, and appreciation condition is: reaction stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1500, volume space velocity 1.5h
-1, use vacuum distillate (VGO) as feedstock oil, feedstock oil character as above table 3.Evaluated under identical process conditions by catalyst FC-1 to FC-7 and FCD-1 to FCD-8, the evaluation result obtained lists in table 4.
Table 3 feedstock oil character
| Feedstock oil | VGO-1 | VGO-2 |
| Density (20 DEG C), g/cm 3 | 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 value | 44.06 | 44.40 |
Table 4 performance evaluation condition and result
| Catalyst | FC-1 | FC-2 | FC-3 | FC-4 | FC-5 | FC-6 | FC-7 |
| Feedstock oil | VGO-1 | VGO-1 | VGO-1 | VGO-1 | VGO-2 | VGO-2 | VGO-2 |
| Volume space velocity during liquid, h -1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| 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 | 367 | 370 | 365 | 363 | 364 | 366 | 371 |
| Product yield and character | |||||||
| Heavy naphtha | |||||||
| Yield, wt% | 8.9 | 9.1 | 7.8 | 7.5 | 7.4 | 6.8 | 8.9 |
| Virtue is dived, wt% | 66.8 | 65.8 | 64.3 | 63.6 | 65.0 | 61.2 | 65.9 |
| Jet fuel | |||||||
| Yield, wt% | 47.9 | 47.6 | 46.5 | 46.7 | 47.9 | 49.6 | 47.8 |
| Smoke point, mm | 27 | 28 | 27 | 28 | 29 | 30 | 28 |
| Aromatic hydrocarbons, v% | 4.6 | 4.5 | 4.8 | 4.7 | 3.9 | 3.1 | 4.9 |
| Diesel oil | |||||||
| Yield, wt% | 22.9 | 22.8 | 23.8 | 22.8 | 22.6 | 23.5 | 22.7 |
| Condensation point, DEG C | -20 | -18 | -17 | -19 | -18 | -22 | -19 |
| Cetane number | 69.7 | 68.6 | 67.5 | 69.5 | 70.9 | 77.9 | 69.8 |
| Tail oil | |||||||
| Yield, wt% | 16.1 | 15.9 | 16.5 | 15.3 | 15.8 | 15.3 | 16.1 |
| Condensation point, DEG C | 11 | 12 | 13 | 12 | 11 | 14 | 12 |
| BMCI value | 11.9 | 12.4 | 12.1 | 13.0 | 12.4 | 9.8 | 12.6 |
| Intermediate oil is selective, wt% | 84.4 | 83.7 | 84.2 | 82.1 | 83.7 | 86.3 | 84.0 |
| Chemical hydrogen consumption, wt% | 2.60 | 2.63 | 2.62 | 2.56 | 2.60 | 2.54 | 2.61 |
Continued 6 performance evaluation condition and result
| Catalyst | FCD-1 | FCD-2 | FCD-3 | FCD-4 | FCD-5 | FCD-6 | FCD-7 | FCD-8 |
| Feedstock oil | VGO-1 | VGO-1 | VGO-1 | VGO-2 | VGO-1 | VGO-1 | VGO-1 | VGO-1 |
| Volume space velocity during liquid, h -1 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| 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 | 375 | 381 | 379 | 385 | 395 | 392 | 386 | 385 |
| Product yield and character | ||||||||
| Heavy naphtha | ||||||||
| Yield, wt% | 11.2 | 12.6 | 13.5 | 12.3 | 13.9 | 12.7 | 13.8 | 11.5 |
| Virtue is dived, wt% | 62.3 | 59.8 | 58.6 | 57.3 | 55.3 | 54.3 | 53.2 | 61.3 |
| Jet fuel | ||||||||
| Yield, wt% | 44.9 | 42.0 | 41.0 | 42.0 | 44.5 | 45.3 | 46.2 | 44.2 |
| Smoke point, mm | 26 | 24 | 25 | 23 | 24 | 24 | 25 | 24 |
| Aromatic hydrocarbons, v% | 4.8 | 5.6 | 6.6 | 8.9 | 8.4 | 5.2 | 5.1 | 4.8 |
| Diesel oil | ||||||||
| Yield, wt% | 22.5 | 21.6 | 20.9 | 18.6 | 21.5 | 21.6 | 20.9 | 22.7 |
| Condensation point, DEG C | -6 | -5 | -4 | -7 | -3 | -7 | -6 | -5 |
| Cetane number | 67.3 | 61.7 | 60.3 | 56.9 | 58.9 | 61.5 | 60.9 | 58.6 |
| Tail oil | ||||||||
| Yield, wt% | 15.1 | 16.1 | 15.9 | 17.3 | 16.5 | 16.3 | 15.5 | 16.0 |
| Condensation point, DEG C | 19 | 20 | 22 | 25 | 26 | 19 | 21 | 22 |
| BMCI value | 14.6 | 15.3 | 15.9 | 15.3 | 14.8 | 14.3 | 14.3 | 15.4 |
| Intermediate oil is selective, wt% | 80.6 | 77.0 | 73.6 | 73.3 | 79.0 | 77.9 | 79.4 | 79.6 |
| Chemical hydrogen consumption, wt% | 2.72 | 2.75 | 2.89 | 2.86 | 2.85 | 2.96 | 2.99 | 2.81 |
As can be seen from the evaluation result of table 4, catalyst prepared by carrier of the present invention under identical process conditions, jet fuel and diesel oil is selective, yield and product quality are all better than reference catalyst.
Claims (20)
1. a carrier of hydrocracking catalyst, comprises beta-molecular sieve, Y zeolite and aluminium oxide, and wherein the character of beta-molecular sieve is as follows: SiO
2/ Al
2o
3mol ratio 30 ~ 150, be preferably 40 ~ 150, non-framework aluminum accounts for less than 2% of total aluminium, accounts for more than 95% of silicon atom in skeleton structure with the silicon atom of Si (0Al) structural coordinates.
2. according to catalyst carrier according to claim 1, it is characterized in that: in described beta-molecular sieve, non-framework aluminum accounts for less than 1% of total aluminium, accounts for 95% ~ 99% of silicon atom in skeleton structure with the silicon atom of Si (0Al) structural coordinates, is preferably 96% ~ 99%.
3. according to catalyst carrier according to claim 1, it is characterized in that: the SiO of described beta-molecular sieve
2/ Al
2o
3mol ratio 60 ~ 120.
4. according to catalyst carrier according to claim 1, it is characterized in that: the relative crystallinity of described beta-molecular sieve is 100% ~ 140%.
5., according to the arbitrary described catalyst carrier of claim 1 ~ 4, it is characterized in that: the meleic acid amount 0.1 ~ 0.5mmol/g of described beta-molecular sieve, NH
3the acid amount of the middle strong acid that-TPD method records accounts for more than 80% of total acid content.
6., according to the arbitrary described catalyst carrier of claim 1 ~ 4, it is characterized in that: meleic acid amount 0.15 ~ 0.45 mmol/g of described beta-molecular sieve, NH
3the acid amount of the middle strong acid that-TPD method records accounts for 85% ~ 95% of total acid content.
7., according to the arbitrary described catalyst carrier of claim 1 ~ 4, it is characterized in that: the Na of described beta-molecular sieve
2o≤0.15wt%, is preferably Na
2o≤0.10wt%.
8., according to the arbitrary described catalyst carrier of claim 1 ~ 4, it is characterized in that: the specific area of described beta-molecular sieve is 400m
2/ g ~ 800m
2/ g, total pore volume is 0.30mL/g ~ 0.50mL/g.
9. according to catalyst carrier according to claim 5, it is characterized in that: the specific area of described beta-molecular sieve is 400m
2/ g ~ 800m
2/ g, total pore volume is 0.30mL/g ~ 0.5mL/g, Na
2o≤0.15wt%.
10. according to catalyst carrier according to claim 1, it is characterized in that: described carrier of hydrocracking catalyst, with the weight of carrier for benchmark, the content of beta-molecular sieve is 5% ~ 20%, the content of Y zeolite is 10% ~ 40%, and the content of aluminium oxide is 40% ~ 85%.
11., according to catalyst carrier according to claim 1, is characterized in that: described Y zeolite, and its character is as follows: specific area is 850m
2/ g ~ 950m
2/ g, total pore volume is 0.43mL/g ~ 0.55mL/g, SiO
2/ Al
2o
3mol ratio is 20 ~ 150, and cell parameter is 2.425 ~ 2.433nm, meleic acid amount 0.1 ~ 0.4mmol/g.
12., according to catalyst carrier according to claim 1, is characterized in that: described support is as follows: specific area is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of the arbitrary described carrier of 13. claims 1 ~ 12, comprising:
By beta-molecular sieve, Y zeolite, aluminium oxide mechanical mixture, shaping, then dry and roasting, makes catalyst carrier; The wherein preparation method of beta-molecular sieve, comprising:
(1) contacted with normal pressure, dynamic water vapour by former for beta-molecular sieve powder, the temperature of contact is 500 ~ 650 DEG C, and the time is 5 ~ 10 hours;
(2) product of step (1) gained contacted with ammonium fluosilicate, then filter, wash and drying, obtain beta-molecular sieve.
14. in accordance with the method for claim 13, it is characterized in that: in step (1), and the former powder of beta-molecular sieve is that template adopts water heat transfer, its SiO with organic amine
2/ Al
2o
3mol ratio 22.5 ~ 28.5, Na
2o content is 1.0wt% ~ 3.0wt%.
15., according to the method described in claim 13 or 14, is characterized in that: in step (1), adopt temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, starts to introduce water vapour, and continue to be warming up to 500 ~ 650 DEG C, then stop 5 ~ 10 hours at this temperature.
16., according to the method described in claim 13 or 14, is characterized in that: in step (1), and water vapour passes through the former powder of beta-molecular sieve by the every kilogram of former powder of beta-molecular sieve 50 ~ 100L/h.
17., according to the method described in claim 13 or 14, is characterized in that: step (1) adopts the 100wt% steam treatment of flowing.
18. according to the method described in claim 13 or 14, it is characterized in that: the concentration of the ammonium fluosilicate aqueous solution that step (2) adopts is 10g ~ 60g/100mL solution, the liquid-solid volume ratio of the ammonium fluosilicate aqueous solution and beta-molecular sieve is 3:1 ~ 15:1; The condition of described contact comprises temperature 40 ~ 120 DEG C, and the time is 0.5 ~ 8.0 hour.
19. in accordance with the method for claim 13, it is characterized in that: the drying condition described in step (2) is as follows: drying 3 ~ 6 hours under the condition of 100 ~ 120 DEG C.
20. in accordance with the method for claim 13, it is characterized in that: drying and the roasting of carrier are as follows: 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 hours.
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| CN103100430A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN103101923A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method thereof |
| CN103447074A (en) * | 2013-09-18 | 2013-12-18 | 中国海洋石油总公司 | Method for preparing hydrocracking catalyst for controlling acidic site distribution |
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| US7517825B2 (en) * | 2007-01-12 | 2009-04-14 | Uop Llc | Aromatic transalkylation using a LZ-210 zeolite |
| CN103100430A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN103101923A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method thereof |
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