CN106732761A - The composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst - Google Patents
The composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst Download PDFInfo
- Publication number
- CN106732761A CN106732761A CN201611144584.5A CN201611144584A CN106732761A CN 106732761 A CN106732761 A CN 106732761A CN 201611144584 A CN201611144584 A CN 201611144584A CN 106732761 A CN106732761 A CN 106732761A
- Authority
- CN
- China
- Prior art keywords
- sba
- beta
- molecular sieves
- solution
- composite molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B01J32/00—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst.The composite molecular screen has the BEA topological structures of micropore Beta molecular sieves and the three-dimensional cubic duct structure of mesopore molecular sieve SBA 16, and its surface area is 600 1000m2·g‑1, aperture is 4 8nm, and pore volume is 0.7 0.9cm3·g‑1.The mixed carrier that the Hydrobon catalyst is made comprising the described composite molecular screens of Beta SBA 16 and alumina support, and Ni and Mo are used as active component.After carrying out hydrofining reaction to FCC diesel feeds oil product using catalyst of the invention, up to 99.2%, sulfur content is less than 10ppm to diesel fuel desulfurization rate, meets the requirement of state V standards.
Description
Technical field
It is made the present invention relates to a kind of Beta-SBA-16 composite molecular screens and preparation method thereof, and the composite molecular screen
Catalyst carrier, and the composite molecular screen is used as Hydrobon catalyst and its preparation method and application obtained in carrier, category
In catalyst technical field.
Background technology
With the development of global economy, the trend of diesel oil of vehicle is accelerated, but simultaneously, SOx in the middle of diesel exhaust,
The problem that NOx and PM (particulate matter) are brought also becomes clear day by day, and the serious environmental pollution such as haze forces environmental regulation increasingly tight
Lattice, diesel quality upgrading paces are accelerated in world wide.Sulfur content in diesel oil is dropped to 15 μ since in the June, 2006 by the U.S.
Below g/g, aromatics quality fraction is less than 35%, and Cetane lndex is more than 40；European countries performed Europe V discharges since 2009
Standard, it is desirable to which the sulfur content in diesel oil is less than 10 μ g/g, Cetane number is more than 51；China will comprehensively supply in 1 day January in 2017
State's V diesel oil of Europe V standards should be equal to, low-sulfur, low aromatic hydrocarbons, the diesel oil of high cetane number turn into the target that oil refining industry is pursued,
Requirement especially to sulfur content is more and more stricter.
At present, hydrogen addition technology is still the most effective means of industrial large-scale production cleaning diesel oil, although anti-by improving
Temperature is answered, reaction velocity is reduced, is increased reactor volume, reduces the various ways such as cut cut point to improve desulfurization depth, but
Improving reaction temperature can increase energy consumption and shorten catalyst service life, and reducing reaction velocity can reduce treating capacity, reconstruction or new
Building device can then increase investment, therefore, the core for being developed into solve problem of high activity deep desulfurization catalyst and main
Means.
Therefore, field is researched and developed in diesel oil hydrofining catalyst, major research and development institutions of the world employ new technology release in succession
A series of high activity diesel deep desulfurization catalyst：" the TK catalyst series " of company, AKZO companies
" the CENTINEL hydrotreating catalysts technology " of " STARS and NEBULA catalyst technologies ", Criterion companies, Chinese stone
Change " the FHUDS catalyst series " of Fushun Petroleum Institute, " the RS series catalysts of Sinopec Research Institute of Petro-Chemical Engineering
Agent " etc..
By the development of decades, the active component of diesel oil hydrofining catalyst relative maturity, and novel carriers
It has been developed into the Main way of Hydrobon catalyst development.The Containing Sulfur of removing is most difficult in deep hydrodesulfurizationof of diesel oil reaction
Compound is the extremely strong dibenzothiophenes class material of steric effect, and this does not require nothing more than catalyst, and there is open pore passage structure to eliminate
Its diffusion effect, also requires that it has suitable acid distribution to strengthen the isomerization desulfurization of alkyl DBT.Therefore, develop to have and open
The carrier of wealthy pore passage structure and appropriate acid matter, the key issue as the exploitation of high-performance diesel hydrogenation for removal sulphur catalyst.
Micro porous molecular sieve as a kind of acid carrier, with specific surface area it is big, acid strong, acid amount is easy to regulate and control, with selecting
The advantages of shape function and good stability, so as to be widely used in the catalytic reaction process in petrochemical industry.But micro-pore zeolite
Less duct limits its application in terms of macromolecules adsorption is separated with catalyzed conversion.And mesoporous material have it is regular
Three-dimensional caged pore passage structure and the characteristics of specific surface area is big, surface apertures are homogeneous and thicker hole wall, this architectural characteristic
Both beneficial to metal active constituent in carrier surface high degree of dispersion, and transmission and expansion beneficial to reactant and product in duct
Dissipate, while catalyst obtains more Active sites raising catalyst activities, also promote product from catalyst surface
It is desorbed so as to improve the selectivity of target product.In recent years, deepening continuously with scientific research, mesopore and micropore composite material is gradually
Focus as people's research.
CN1513951A discloses one kind and prepares hydrodesulfurization catalytic using novel carriers material carrying metal active component
The preparation method of agent, wherein, novel carriers material is the complex carrier that micro porous molecular sieve and mesoporous molecular sieve are constituted.Micropore point
Son sieve is Y zeolites, ZSM-5 zeolite, Beta zeolites, type A zeolite etc., and mesoporous molecular sieve is MCM-41, SBA-15 and SBA-16
Deng.In embodiment, although including Beta zeolites and SBA-16 mesoporous materials in complex carrier, its preparation method is machine
Tool mixes, and can not give full play to reactant in the adjustable advantage of Beta acidic zeolites, and mesopore molecular sieve macropore structure
The diffusion advantage of molecule.
CN102199068A discloses a kind of preparation method of Jie's micropore complex type molecular sieve catalysis, wherein microporous molecular
It is H type Beta zeolites to sieve, and mesopore molecular sieve is MCM-41.By experimental verification, the Im3m three-dimensional cubics duct of SBA-16 with
The P6mm two dimension hexagonal holes road structure of MCM-41 is compared, and its diffusion can be improved significantly.Because SBA-16 is mesoporous
Material has the connecting hole and substantial amounts of branch pore network in connection main aperture road such that it is able to for molecule provides more favorably diffusion
Condition, can further improve its catalyst-loaded catalytic performance.
The content of the invention
It is an object of the invention to provide a kind of Beta-SBA-16 composite molecular screens and preparation method thereof.The composite molecular screen
With excellent pore structure (high-specific surface area, large aperture).The composite molecular screen is made mixed carrier and hydrogenation essence is applied to
The preparation of catalyst processed, hydrofinishing can be carried out using the catalyst to FCC diesel feeds oil product.
It is yet another object of the invention to provide the catalyst carrier that a kind of above-mentioned Beta-SBA-16 composite molecular screens are made.
It is hydrogenated with as obtained in carrier it is yet another object of the invention to provide a kind of above-mentioned Beta-SBA-16 composite molecular screens
Catalyst for refining and preparation method thereof.
It is yet another object of the invention to provide above-mentioned Hydrobon catalyst hydrofinishing is carried out in FCC diesel feeds oil product
Application in reaction.
To reach above-mentioned purpose, present invention firstly provides a kind of Beta-SBA-16 composite molecular screens, the composite molecular screen
Three-dimensional cubic (Im3m) pore passage structure of BEA topological structures and mesopore molecular sieve SBA-16 with micropore Beta molecular sieves, its
Surface area is 600-1000m2·g-1, aperture is 4-8nm, and pore volume is 0.7-0.9cm3·g-1。
The Beta-SBA-16 composite molecular screens that the present invention is provided have the micropore and SBA-16 molecular sieves of Beta molecular sieves
Mesoporous dual pore passage structure, is a kind of compound Jie's micro porous molecular sieve.Jie of the Beta-SBA-16 composite molecular screens that the present invention is provided
There is primary, the secondary structure unit of Beta molecular sieves in the hole wall of hole, be not single micro porous molecular sieve and mesopore molecular sieve
Mechanical mixture, therefore it is called compound Jie's micro porous molecular sieve.And the present invention is by the compound of Jie's micropore, using Beta molecular sieves
Primary, secondary structure unit carry out modulation to acidity, and make full use of the mass-transfer performance of mesopore orbit, it is therefore resulting
Composite molecular screen can obtain suitable acidity, it is also possible to retain the duct advantage of mesopore molecular sieve.
Additionally, present invention also offers a kind of preparation method of above-mentioned Beta-SBA-16 composite molecular screens, the method bag
Include following steps：
(1) Beta molecular sieve crystallite emulsion presomas are prepared using nano microcrystalline self-assembly method；
(2) with F127 (EO106PO70EO106) it is template, tetraethyl orthosilicate (TEOS) is silicon source, prepares SBA-16 and is situated between
The precursor solution of porous molecular sieve；
(3) to adding the Beta molecular sieves crystallite emulsion forerunner in the precursor solution of the SBA-16 mesopore molecular sieves
Body, stirring 18-24h is obtained mixed solution, by the mixed solution in 80-140 DEG C of crystallization 24-60h, then scrubbed, dry,
Roasting, is obtained described Beta-SBA-16 composite molecular screens.
In above-mentioned preparation method, it is preferable that the Beta molecular sieves crystallite emulsion presoma is through the following steps that system
For what is obtained：By raw material tetraethyl orthosilicate (TEOS), tetraethyl ammonium hydroxide (TEAOH), H2O, NaOH and sodium metaaluminate
According to (1.0-2.0) Na2O：Al2O3：(20-60)SiO2：(200-400)H2The mol ratio of O is (more preferably according to (1.0-2.0)
Na2O：Al2O3：(20-60)SiO2：(200-350)H2The mol ratio of O) it is well mixed after, in 100-140 DEG C of crystallization 18-24h, system
It is standby to obtain described Beta molecular sieve crystallite emulsion presomas.
More specifically, the Beta molecular sieves crystallite emulsion presoma is through the following steps that prepare：
Step one：With tetraethyl orthosilicate, tetraethyl ammonium hydroxide, H2O, NaOH and sodium metaaluminate, will used as raw material
After a part of tetraethyl orthosilicate in raw material mixes with whole tetraethyl ammonium hydroxides, stir to transparent, obtain one first molten
Liquid；
Step 2：By remaining tetraethyl orthosilicate in raw material and whole H2After O, NaOH and sodium metaaluminate mixing, stir
Mix to dissolving, obtain one second solution；
Step 3：Second solution is added dropwise in first solution, stirring 2-4h is until what is formed is molten
Glue is no longer layered, and in 100-140 DEG C of crystallization 18-24h, prepares described Beta molecular sieve crystallite emulsion presomas；
Wherein, raw material tetraethyl orthosilicate, tetraethyl ammonium hydroxide, H2O, NaOH and sodium metaaluminate meet (1.0-
2.0)Na2O：Al2O3：(20-60)SiO2：(200-400)H2The mol ratio of O, preferably meets (1.0-2.0) Na2O：Al2O3：(20-
60)SiO2：(200-350)H2The mol ratio of O.
In above-mentioned preparation method, it is preferable that the SiO of the Beta molecular sieves crystallite emulsion presoma2/Al2O3Mol ratio
It is (20-60)：1, more preferably (24-36)：1.
In above-mentioned preparation method, it is preferable that the precursor solution of the SBA-16 mesopore molecular sieves is by following step
Suddenly prepare：By raw material F127 (EO106PO70EO106), HCl solution (concentration is preferably 2.0M), n-butanol and positive silicic acid four
Ethyl ester (TEOS) is according to F127：N-butanol：Tetraethyl orthosilicate：HCl：H2O=0.004：2.0：1.0：(1.5-6.0)：140
After mixed in molar ratio is uniform, the precursor solution of SBA-16 mesopore molecular sieves is prepared.It is highly preferred that each raw material is mixed into equal
It is even to be carried out under the conditions of 28-40 DEG C, and the precursor solution of the SBA-16 mesopore molecular sieves H+Concentration is
1.0mol/L~2.5mol/L.
More specifically, the precursor solution of the SBA-16 mesopore molecular sieves is through the following steps that prepare：
Step one：Using hydrothermal synthesis method, by F127 and HCl solution (concentration is preferably 2.0M), in 28-40 DEG C of stirring
1.5-2.5h；
Step 2：After after solution clear, n-butanol is added, continue to stir 0.5-1.5h at 28-40 DEG C；
Step 3：TEOS is added dropwise under stirring, after continuing to stir 1.5-2.5h at 28-40 DEG C, is prepared
The precursor solution of described SBA-16 mesopore molecular sieves, and the precursor solution of the SBA-16 mesopore molecular sieves H+It is dense
It is 1.0mol/L~2.5mol/L to spend；
Wherein, raw material F127, HCl solution, n-butanol and TEOS meet F127：N-butanol：TEOS：HCl：H2O=
0.004：2.0：1.0：(1.5-6.0)：140 mol ratio.
In above-mentioned preparation method, it is preferable that the precursor solution and the Beta of the SBA-16 mesopore molecular sieves point
Son sieve crystallite emulsion presoma mixed proportion be：Raw material F127 in the precursor solution of SBA-16 mesopore molecular sieves：Beta
The mass ratio of molecular sieve crystallite emulsion presoma is 1：(1-2.5).
In above-mentioned preparation method, it is preferable that step (3) is under the rapid mixing conditions of 3r/s~10r/s, to described
The Beta molecular sieves crystallite emulsion presoma is added dropwise in the precursor solution of SBA-16 mesopore molecular sieves.
In the preparation method of Beta-SBA-16 composite molecular screens of the invention, the presoma of SBA-16 mesopore molecular sieves
The synthesis of the composite molecular screen of different silica alumina ratios can be used for as silicon source using TEOS in the building-up process of solution.Additionally,
Beta molecular sieve crystallite emulsion presomas synthesize at normal temperatures, and complete crystallization at 100-140 DEG C.Also, Beta-SBA-16 is answered
The synthesis for closing molecular sieve is carried out static under the conditions of pressing.
The Beta-SBA-16 composite molecular screen preparation methods that the present invention is provided, have the characteristics that：Using under cryogenic conditions
Synthesis, composite molecular screen preferably maintains the average pore size and specific surface area of meso-porous molecular sieve material, and composite molecular screen
With three-dimensional cubic structure, be conducive to improving the diffusion and metal dispersion performance of corresponding catalyst；Beta- of the invention
SBA-16 composite molecular screens have suitable acidity, are conducive to the carrying out of hydrofining reaction.
In addition, present invention also offers the catalyst carrier that a kind of above-mentioned Beta-SBA-16 composite molecular screens are made.
Specific embodiment of the invention, it is preferable that the catalyst carrier is through the following steps that prepare
's：Ion-exchange treatment is carried out to described Beta-SBA-16 composite molecular screens, by the composite molecular screen after ion-exchange treatment
Mixed carrier, as described catalyst carrier are made with alumina support.
In said catalyst carrier, it is preferable that the alumina support is in 4-6h using boehmite from room temperature
Time-program(me) be warming up to 500 DEG C -550 DEG C, then constant temperature calcining 5-7h and prepare.
In said catalyst carrier, it is preferable that Beta-SBA-16 composite molecular screens are with the mass ratio of alumina support
(0.2-0.4)：1, more preferably (0.2-0.3)：1.
In said catalyst carrier, the tool of ion-exchange treatment is carried out to described Beta-SBA-16 composite molecular screens
Body step and the specific steps for being made mixed carrier with alumina support can be that this area is conventional.
Additionally, smart as being hydrogenated with obtained in carrier present invention also offers a kind of above-mentioned Beta-SBA-16 composite molecular screens
Catalyst processed.
Specific embodiment of the invention, it is preferable that the Hydrobon catalyst includes described Beta-SBA-
The mixed carrier that 16 composite molecular screens and alumina support are made, and Ni and Mo are used as active component.It is highly preferred that described
In mixed carrier, Beta-SBA-16 composite molecular screens are (0.2-0.4) with the mass ratio of alumina support：1, particularly preferably for
(0.2-0.3)：1；On the basis of the gross weight of the Hydrobon catalyst, the content of Ni is calculated as 3%-4% with NiO, Mo's
Content is with MoO3It is calculated as 8%-15%.
Invention further provides a kind of preparation method of above-mentioned Hydrobon catalyst, the method is comprised the following steps：
(1) ion-exchange treatment is carried out to described Beta-SBA-16 composite molecular screens, by ion-exchange treatment after answer
Close molecular sieve and be made mixed carrier with alumina support；
(2) and then by active metal step impregnation to mixed carrier, then through drying, roasting, described hydrogenation essence is obtained
Catalyst processed.
In the preparation method of above-mentioned Hydrobon catalyst, it is preferable that the alumina support is using the thin water aluminium of plan
Stone is warming up to 500 DEG C -550 DEG C from room temperature in the time-program(me) of 4-6h, then constant temperature calcining 5-7h and prepare.
In the preparation method of above-mentioned Hydrobon catalyst, it is preferable that in the mixed carrier, ion-exchange treatment
Beta-SBA-16 composite molecular screens afterwards are (0.2-0.4) with the mass ratio of alumina support：1, more preferably (0.2-0.3)：
1。
In the preparation method of above-mentioned Hydrobon catalyst, it is preferable that the active metal includes Ni and Mo.More preferably
Ground, on the basis of the gross weight of the Hydrobon catalyst, the content of Ni is calculated as 3%-4% with NiO, and the content of Mo is with MoO3
It is calculated as 8%-15%.
In the preparation method of above-mentioned Hydrobon catalyst, described Beta-SBA-16 composite molecular screens are carried out from
The specific steps and alumina support that son exchanges treatment are made the specific steps of mixed carrier, arrive active metal step impregnation
Specific steps on mixed carrier and drying afterwards, the temperature of roasting can be that this area is conventional.
Due to aluminum oxide and the active metal stronger interaction of presence, and composite molecular screen is weaker with active metal presence
Interaction, these all can seriously hinder the activity of catalyst.The present invention is by by alumina support and compound molecule sieve series
Into mixed carrier, the mixed carrier can balanced this interaction, and then make the catalyst of preparation that there is good activity.
Invention further provides above-mentioned Hydrobon catalyst in FCC diesel feeds oil product carries out hydrofining reaction
Using.
Dashed forward using Beta-SBA-16 composite molecular screens as the obtained Hydrobon catalyst performance of a part for mixed carrier
Go out, hydrofining reaction, highest desulfurization degree are carried out to FCC diesel feeds oil product using described catalyst>99.2%.
In sum, the invention provides a kind of Beta-SBA-16 composite molecular screens and its obtained mixed carrier and
The Hydrobon catalyst prepared using the mixed carrier and its application.The Beta-SBA-16 composite molecular screens that the present invention is provided
The mesoporous dual pore passage structure of micropore and SBA-16 molecular sieves with Beta molecular sieves, is a kind of compound Jie's micro porous molecular sieve,
Its surface area is 600-1000m2·g-1, aperture is 4-8nm, and pore volume is 0.7-0.9cm3·g-1.The hydrogenation essence that the present invention is provided
Catalyst processed includes mixed carrier, a kind of Ni metals of VIII race and one kind of Beta-SBA-16 composite molecular screens and aluminum oxide
VI B races Mo metals are used as active component.After hydrofining reaction being carried out using described catalyst to FCC diesel feeds oil product,
Up to 99.2%, sulfur content is less than 10ppm to diesel fuel desulfurization rate, meets the requirement of state V standards.
Brief description of the drawings
Fig. 1 is the small angle XRD spectra of the sample that Beta-SBA-16 composite molecular screens silica alumina ratio obtained in embodiment 1 is 50；
Fig. 2 is the wide-angle XRD spectra of the sample that Beta-SBA-16 composite molecular screens silica alumina ratio obtained in embodiment 1 is 50；
Fig. 3 a-3c are respectively pure SBA-16 mesopore molecular sieves, Beta-SBA-16 composite molecular screens silicon obtained in embodiment 1
Aluminum ratio is the transmission electron microscope picture of 50 or 60 sample；
Fig. 4 is the N of Beta-SBA-16 composite molecular screens obtained in embodiment 12- adsorption/desorption isotherms figure；
Fig. 5 is the graph of pore diameter distribution of Beta-SBA-16 composite molecular screens obtained in embodiment 1.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Embodiment 1
Serial Beta-SBA-16 composite molecular screens are present embodiments provided, their preparation process is comprised the following steps：
First, Beta molecular sieve crystallite emulsion presomas are prepared
Step one：Take 26.0g TEAOH to be added in 21.43g TEOS, dissolve at room temperature, 30min is to transparent for stirring,
It is designated as solution (1)；
Step 2：By 0.19g NaOH, NaAlO2, 3.50g TEAOH and 2g H2O mixes, stirring to dissolving, according to multiple
Molecular sieve difference silica alumina ratio Si/Al=30,40,50,60 are closed, different amounts of NaAlO is added2, respectively：1.1519g、
0.8639g, 0.6912g, 0.5760g, are designated as solution (2)；
Step 3：Solution (2) is added dropwise in solution (1), stirring 2-4h is until the colloidal sol for being formed no longer is layered；
Step 4：It is transferred in crystallizing kettle, in 140 DEG C of crystallization 24h, pressure is about 0.4-0.5MPa, crystallization in crystallizing kettle
After the completion of, serial Beta molecular sieves crystallite emulsion presoma is obtained final product, it is standby.
2nd, the precursor solution of SBA-16 mesopore molecular sieves is prepared
Step one：At 35 DEG C, 4g templates F127 is added in the 2mol/L HCl solutions of 240mL, stirring and dissolving, remembered
It is solution (3)；
Step 2：To 12g n-butanols are added in solution (3), continue to stir 1h, be then added dropwise over 16.6g TEOS, after
Continuous stirring 2h, wherein, the mol ratio of raw material dosage is F127：N-butanol：TEOS：HCl：H2O=0.004：2.0：1.0：6.0：
140, obtain the precursor solution of SBA-16 mesopore molecular sieves.
3rd, glue is mixed：Under the quick stirring of 3r/s~10r/s, to the precursor solution of above-mentioned SBA-16 mesopore molecular sieves
It is middle to be added dropwise over the above-mentioned serial Beta molecular sieves crystallite emulsion presomas of 8.0g respectively, collosol state is formed after stirring 24h, it is obtained
Serial mixed solution.
4th, hydrothermal crystallizing：Serial mixed solution is transferred in crystallizing kettle respectively, the crystallization 60h in 120 DEG C of baking ovens；So
By washing, 80 DEG C dry 12h, 550 DEG C roasting 6h, cool, obtain serial Beta-SBA-16 composite molecular screens, respectively
(therein 30,40,50,60 represent the silica alumina ratio Si/ of composite molecular screen to be designated as BS-30, BS-40, BS-50, BS-60
Al)。
Test analysis are carried out to the sample that silica alumina ratio in above-mentioned serial Beta-SBA-16 composite molecular screens is 50, its is small
Angle XRD, wide-angle XRD results difference are as shown in Figure 1 and Figure 2.Pure SBA-16 mesopore molecular sieves, the transmission electron microscope of BS-50, BS-60
(TEM) as shown in figs 3 a-3 c, wherein Fig. 3 a are the transmission electron microscope picture of pure SBA-16 mesopore molecular sieves to figure difference, and Fig. 3 b are sial
Than the transmission electron microscope picture that the Beta-SBA-16 for 50 is combined Jie's micro porous molecular sieve, Fig. 3 c are Beta-SBA-16 that silica alumina ratio is 60
The transmission electron microscope picture of compound Jie's micro porous molecular sieve.BS-30, BS-40, BS-50, BS-60 and tradition γ-Al2O3N2- absorption
Desorption isotherm is as shown in Figure 4.BS-30, BS-40, BS-50, BS-60 and tradition γ-Al2O3Pore-size distribution such as Fig. 5 institutes
Show.
Test draws Beta-SBA-16 composite molecular screens BS-30, BS-40, BS-50, BS-60 obtained in the present embodiment
Pore structure parameter is as shown in table 1.
Table 1
Embodiment 2
Serial Hydrobon catalyst is present embodiments provided, their preparation method is comprised the following steps：
First, the H type Beta-SBA-16 composite molecular screen carriers after ion-exchange treatment are prepared
By series Beta-SBA-16 composite molecular screens obtained in embodiment 1 respectively with the NH of 1mol/L4Cl solution is according to 1g
Composite molecular screen correspondence 10mL NH4The ratio of Cl solution stirs 2h under 80 DEG C of water bath conditions and carries out ammonium exchange, through filtering, washing
Wash, dry, then carrying out second ammonium exchange with same steps can obtain serial H types Beta-SBA-16 composite molecular screens load
Body.
2nd, mixed carrier is prepared
Using mechanical mixing by above-mentioned serial H types Beta-SBA-16 composite molecular screens carrier respectively with γ-Al2O3With matter
Amount compares 1:4 ratio is mixed to prepare serial Beta-SBA-16- γ-Al2O3Mixed carrier (is designated as BSA).
3rd, Hydrobon catalyst is prepared
Step one：0.71g ammonium molybdates are dissolved in deionized water wiring solution-forming, impregnating serial BSA respectively using the solution mixes
Carrier (5g) is closed, while ultrasonic wave disperses 15 minutes, stirring dries 5h at 100 DEG C after 3 minutes, after 550 DEG C of roasting 6h, cooling
To room temperature, prepared series has loaded the Mo/BSA carriers of molybdenum；
Step 2：Deionized water wiring solution-forming is dissolved in 0.79g nickel nitrates, above-mentioned series is impregnated respectively using the solution
Mo/BSA carriers, while ultrasonic wave disperses 15 minutes, stirring is drying 5h at 100 DEG C after 3 minutes, after 550 DEG C of roasting 6h, cooling
To room temperature, prepared series has loaded molybdenum and the Hydrobon catalyst of nickel (is designated as Cat-BSA-x, x=30,40,50,60；Wherein
X represents the silica alumina ratio Si/Al of the H type Beta-SBA-16 composite molecular screen carriers in mixed carrier)；
After tested, in above-mentioned serial Hydrobon catalyst, Mo is with MoO3Meter, mass fraction is 10%；Ni in terms of NiO,
Mass fraction is 3.5%.
Test case 1
Reaction raw materials property is as shown in table 2.
The some properties of the FCC diesel raw materials of table 2
It is charging oil product to use FCC diesel oil, and the catalyst with embodiment 2 carries out hydrofining reaction condition as refining agent
Optimization, has investigated feed stock conversion, product slates and yield.
The method that specific test is carried out to catalyst is as follows：
(1) Catalyst packing：Silica wool+quartz sand (20-40 mesh) 14mL+ silica wools+refining agent 2g+ silica wools+quartz
Sand 6mL+ silica wools；
(2) pre-vulcanization process condition：320 DEG C of temperature, pressure 4MPa, vulcanization flow quantity is 2.5mL/h, stabilization 4h；
(3) evaluation procedure reaction condition：Reaction temperature is 350 DEG C, pressure 5MPa, mass space velocity 1.0h-1, hydrogen-oil ratio 600.
Catalyst hydrogenation refining reaction result is as shown in table 3.
The catalyst hydrogenation refining reaction result of table 3
As can be seen from Table 3, Cat-BSA-30, Cat-BSA-40, Cat-BSA-50, Cat-BSA-60 are to FCC diesel oil
Hydrofinishing effect is all higher than with traditional γ-Al2O3It is the Cat-Al of carrier2O3, the desulfurization performance highest of Cat-BSA-50, product
The sulfur content of thing is less than 10ppm, has reached " state V " standard.
Claims (10)
1. a kind of Beta-SBA-16 composite molecular screens, the composite molecular screen have micropore Beta molecular sieves BEA topological structures and
The three-dimensional cubic duct structure of mesopore molecular sieve SBA-16, its surface area is 600-1000m2·g-1, aperture is 4-8nm, pore volume
It is 0.7-0.9cm3·g-1。
2. a kind of preparation method of the Beta-SBA-16 composite molecular screens described in claim 1, the method is comprised the following steps：
(1) Beta molecular sieve crystallite emulsion presomas are prepared using nano microcrystalline self-assembly method；
(2) with F127 as template, tetraethyl orthosilicate is silicon source, prepares the precursor solution of SBA-16 mesopore molecular sieves；
(3) to adding the Beta molecular sieves crystallite emulsion presoma in the precursor solution of the SBA-16 mesopore molecular sieves,
Stirring 18-24h is obtained mixed solution, by the mixed solution in 80-140 DEG C of crystallization 24-60h, then scrubbed, dry, roasting
Burn, described Beta-SBA-16 composite molecular screens are obtained.
3. preparation method according to claim 2, wherein, the Beta molecular sieves crystallite emulsion presoma is by following
What step was prepared：By raw material tetraethyl orthosilicate, tetraethyl ammonium hydroxide, H2O, NaOH and sodium metaaluminate according to
(1.0-2.0)Na2O：Al2O3：(20-60)SiO2：(200-400)H2After the mixed in molar ratio of O is uniform, in 100-140 DEG C of crystallization
18-24h, prepares described Beta molecular sieve crystallite emulsion presomas；
Preferably, the Beta molecular sieves crystallite emulsion presoma is through the following steps that prepare：
Step one：With tetraethyl orthosilicate, tetraethyl ammonium hydroxide, H2O, NaOH and sodium metaaluminate as raw material, by raw material
A part of tetraethyl orthosilicate mix with whole tetraethyl ammonium hydroxides after, stirring obtains one first solution to transparent；
Step 2：By remaining tetraethyl orthosilicate in raw material and whole H2After O, NaOH and sodium metaaluminate mixing, stirring is to molten
Solution, obtains one second solution；
Step 3：Second solution is added dropwise in first solution, stirring 2-4h until the colloidal sol that is formed not
It is layered again, in 100-140 DEG C of crystallization 18-24h, prepares described Beta molecular sieve crystallite emulsion presomas；
Wherein, raw material tetraethyl orthosilicate, tetraethyl ammonium hydroxide, H2O, NaOH and sodium metaaluminate meet (1.0-2.0)
Na2O：Al2O3：(20-60)SiO2：(200-400)H2The mol ratio of O.
4. the preparation method according to Claims 2 or 3, wherein, the SiO of the Beta molecular sieves crystallite emulsion presoma2/
Al2O3Mol ratio is (20-60)：1, preferably (24-36)：1.
5. preparation method according to claim 2, wherein, the precursor solution of the SBA-16 mesopore molecular sieves is to pass through
What following steps were prepared：By raw material F127, HCl solution, n-butanol and tetraethyl orthosilicate according to F127：N-butanol：Just
Tetraethyl orthosilicate：HCl：H2O=0.004：2.0：1.0：(1.5-6.0)：After 140 mixed in molar ratio is uniform, prepare
The precursor solution of SBA-16 mesopore molecular sieves；
Preferably, each raw material is well mixed is carried out under the conditions of 28-40 DEG C, and the SBA-16 mesopore molecular sieves
The H of precursor solution+Concentration is 1.0mol/L~2.5mol/L.
6. preparation method according to claim 2, wherein, the precursor solution of the SBA-16 mesopore molecular sieves and described
The mixed proportion of Beta molecular sieve crystallite emulsion presomas is：Raw material in the precursor solution of SBA-16 mesopore molecular sieves
F127：The mass ratio of Beta molecular sieve crystallite emulsion presomas is 1：(1-2.5).
7. the catalyst carrier that the Beta-SBA-16 composite molecular screens described in a kind of claim 1 are made.
8. the Beta-SBA-16 composite molecular screens described in a kind of claim 1 are used as Hydrobon catalyst obtained in carrier.
9. a kind of preparation method of the Hydrobon catalyst described in claim 8, the method is comprised the following steps：
(1) ion-exchange treatment is carried out to described Beta-SBA-16 composite molecular screens, by ion-exchange treatment after compound point
Son sieve is made mixed carrier with alumina support；
(2) and then by active metal step impregnation to mixed carrier, then through drying, roasting, described hydrofinishing is obtained and urges
Agent；
Preferably, in the mixed carrier, Beta-SBA-16 composite molecular screens and alumina support after ion-exchange treatment
Mass ratio be (0.2-0.4)：1, more preferably (0.2-0.3)：1；
The active metal includes Ni and Mo；It is highly preferred that on the basis of the gross weight of the Hydrobon catalyst, Ni's contains
Amount is calculated as 3%-4% with NiO, and the content of Mo is with MoO3It is calculated as 8%-15%.
10. the Hydrobon catalyst described in a kind of claim 8 is in FCC diesel feeds oil product carries out hydrofining reaction
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611144584.5A CN106732761A (en) | 2016-12-13 | 2016-12-13 | The composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611144584.5A CN106732761A (en) | 2016-12-13 | 2016-12-13 | The composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106732761A true CN106732761A (en) | 2017-05-31 |
Family
ID=58880653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611144584.5A Pending CN106732761A (en) | 2016-12-13 | 2016-12-13 | The composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732761A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108393096A (en) * | 2018-03-20 | 2018-08-14 | 中国海洋石油集团有限公司 | Hydrobon catalyst, the grading composition method of Hydrobon catalyst and application |
| CN109225332A (en) * | 2018-08-24 | 2019-01-18 | 中国石油大学(华东) | A kind of preparation method for Desulphurization of fuels catalyst |
| CN112320813A (en) * | 2019-08-05 | 2021-02-05 | 中国石油化工股份有限公司 | Preparation method and application of amino-functionalized SBA molecular sieve |
| CN113019440A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrofining catalyst carrier, hydrofining catalyst and preparation method thereof |
| CN113019422A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof |
| CN113019437A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
| CN113023745A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Beta/Al-SBA-15 composite molecular sieve and preparation method and application thereof |
| CN114195165A (en) * | 2020-09-17 | 2022-03-18 | 中国石油天然气股份有限公司 | Composite carrier with step pore structure distribution and preparation method thereof |
| CN114308116A (en) * | 2021-12-23 | 2022-04-12 | 复旦大学 | Nano nickel-based MFI (melt flow index) crystallite molecular sieve and preparation method and application thereof |
| CN114453016A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst, hydrotreating catalyst and application |
| CN114453018A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof |
| CN114453017A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN114453012A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst, hydrocracking catalyst and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774855A (en) * | 2011-05-12 | 2012-11-14 | 北京化工大学 | Preparation method of microporous-mesoporous composite zeolite |
| CN103100399A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of mesoporous-microporous composite molecular sieve |
| CN104588091A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Beta and EU-1 composite molecular sieve and synthesis method thereof |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
-
2016
- 2016-12-13 CN CN201611144584.5A patent/CN106732761A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774855A (en) * | 2011-05-12 | 2012-11-14 | 北京化工大学 | Preparation method of microporous-mesoporous composite zeolite |
| CN103100399A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of mesoporous-microporous composite molecular sieve |
| CN104588091A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Beta and EU-1 composite molecular sieve and synthesis method thereof |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
Non-Patent Citations (1)
| Title |
|---|
| DAOW EI GAO ET AL.: "Self-assembly of monodispersed hierarchically porous Beta-SBA-15 with different morphologies and its hydro-upgrading performances for FCC gasoline", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108393096A (en) * | 2018-03-20 | 2018-08-14 | 中国海洋石油集团有限公司 | Hydrobon catalyst, the grading composition method of Hydrobon catalyst and application |
| CN108393096B (en) * | 2018-03-20 | 2021-03-02 | 中国海洋石油集团有限公司 | Hydrodesulfurization catalyst, grading combination method of hydrofining catalyst and application |
| CN109225332A (en) * | 2018-08-24 | 2019-01-18 | 中国石油大学(华东) | A kind of preparation method for Desulphurization of fuels catalyst |
| CN112320813A (en) * | 2019-08-05 | 2021-02-05 | 中国石油化工股份有限公司 | Preparation method and application of amino-functionalized SBA molecular sieve |
| CN112320813B (en) * | 2019-08-05 | 2023-05-09 | 中国石油化工股份有限公司 | Preparation method and application of amino-functionalized SBA molecular sieve |
| CN113019437A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
| CN113019440A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrofining catalyst carrier, hydrofining catalyst and preparation method thereof |
| CN113023745A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Beta/Al-SBA-15 composite molecular sieve and preparation method and application thereof |
| CN113019422A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof |
| CN113019437B (en) * | 2019-12-25 | 2023-01-10 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
| CN113019422B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof |
| CN113019440B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrofining catalyst carrier, hydrofining catalyst and preparation method thereof |
| CN113023745B (en) * | 2019-12-25 | 2022-08-12 | 中国石油化工股份有限公司 | Beta/Al-SBA-15 composite molecular sieve and preparation method and application thereof |
| CN114195165A (en) * | 2020-09-17 | 2022-03-18 | 中国石油天然气股份有限公司 | Composite carrier with step pore structure distribution and preparation method thereof |
| CN114195165B (en) * | 2020-09-17 | 2023-08-22 | 中国石油天然气股份有限公司 | Composite carrier with step hole structure distribution and preparation method thereof |
| CN114453012A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst, hydrocracking catalyst and application |
| CN114453017A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN114453018A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method thereof |
| CN114453016A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst, hydrotreating catalyst and application |
| CN114453012B (en) * | 2020-10-21 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst, hydrocracking catalyst and application |
| CN114453016B (en) * | 2020-10-21 | 2023-08-01 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst, hydrotreating catalyst and application |
| CN114453018B (en) * | 2020-10-21 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier, hydrocracking catalyst and preparation method of hydrocracking catalyst |
| CN114453017B (en) * | 2020-10-21 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN114308116A (en) * | 2021-12-23 | 2022-04-12 | 复旦大学 | Nano nickel-based MFI (melt flow index) crystallite molecular sieve and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732761A (en) | The composite molecular screens of Beta SBA 16 and its obtained Hydrobon catalyst | |
| CN105251527B (en) | A kind of composite molecular screen and the Hydrobon catalyst made of it is as carrier | |
| JP5292301B2 (en) | Catalysts based on silicon-containing materials with hierarchical porosity and process for hydrocracking / hydroconversion and hydroprocessing of hydrocarbon feeds | |
| US10265687B2 (en) | Na—Y molecular sieve, H—Y molecular sieve, and preparation methods thereof, hydrocracking catalyst, and hydrocracking method | |
| CN107971001B (en) | It is a kind of to contain the assistant for calalytic cracking and preparation method thereof for being rich in mesoporous Beta molecular sieve | |
| CN102895948B (en) | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof | |
| Du et al. | Synthesis of a novel micro/mesoporous composite material Beta-FDU-12 and its hydro-upgrading performance for FCC gasoline | |
| CN107971011B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN107971016B (en) | A kind of catalytic cracking catalyst and preparation method thereof containing phosphorous IMF structure molecular screen | |
| CN100469447C (en) | Macropore catalytic cracking catalyst synthesized by granular formwork method | |
| CN107971000A (en) | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof | |
| CN107970978B (en) | Phosphorus-containing and metal-loaded MFI structure molecular sieve and preparation method thereof | |
| CN107973308B (en) | Phosphorus-containing MFI structure molecular sieve and preparation method thereof | |
| CN107345155B (en) | A kind of method for hydrogen cracking | |
| Zhang et al. | Effect of cerium ions initial distribution on the crystalline structure and catalytic performance of CeY zeolite | |
| CN107345154B (en) | A kind of method for hydrogen cracking of poor ignition quality fuel | |
| CN112047358A (en) | Zinc or/and nickel-containing ZSM-5 molecular sieve with multi-stage structure and preparation method and application thereof | |
| CN107344102B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN102895947A (en) | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof | |
| CN114433252B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN114425421B (en) | Catalytic cracking catalyst and preparation method and application thereof | |
| CN114477226B (en) | Composite molecular sieve and hydro-upgrading catalyst prepared by using same as carrier | |
| US10828626B2 (en) | Composite material | |
| CN107345159B (en) | A kind of method for hydrogen cracking producing low-coagulation diesel oil | |
| Hu et al. | Characteristics of zeolite‐modified NiMo/Al2O3 catalysts and their hydrotreating performance for light cycled oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180503 Address after: 100010 room 1414, Hai Yuan building, 25 Chaoyangmen North Street, Dongcheng District, Beijing. Applicant after: China Offshore Oil Group Co., Ltd. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Applicant after: CNOOC ( Qingdao) Heavy Oil Processing Engineering Technology Research Center Co.,Ltd. Applicant after: China University of Petroleum (Beijing) Address before: 102209 the 7 floor of block C in the sea oil plant of the future technology city of Changping District, Beijing. Applicant before: CNOOC Refining & Chemical Research Institute (Beijing) Co., Ltd. Applicant before: China University of Petroleum (Beijing) |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |