CN104624227A - Mesoporous-microporous molecular sieve hydrocracking catalyst - Google Patents
Mesoporous-microporous molecular sieve hydrocracking catalyst Download PDFInfo
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Abstract
The invention relates to a mesoporous-microporous molecular sieve hydrocracking catalyst. The catalyst comprises aluminium oxide, an acidic component and hydrogenated active metal, wherein the acidic component comprises a USY molecular sieve with super-low sodium oxide and potassium oxide content and a modified ZSM-5 molecular sieve. Amodification method of the modified ZSM-5 molecular sieve comprises the steps of treating ZSM-5 with mixed bases, then treating a treated and roasted sample with an organic acid and rare earth solution and finally performing filtering, washing and drying to obtain a modified sample. Accordingto the catalyst, when mesopores are processed in theZSM-5 molecular sieve, a microporous structure is reserved to the maximum extent, the specific surface area is increased to the maximum extent, and the damage degree of a frame is reduced. Thecatalyst can be used for producing tail oil, heavy naphtha and diesel oil and has the characteristics of high total yield of tail oil and heavy naphtha, low condensation point of diesel oiland low BMCI value of tail oil.
Description
Technical field
The present invention relates to a kind of mesoporous-micro porous molecular sieve hydrocracking catalyst.Catalyst composition comprises aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of ultra-low oxidized sodium, the USY molecular sieve of potassium oxide content and the composite modified ZSM-5 molecular sieve of one, belong to catalyst technical field.
Background technology
ZSM-5 type zeolite molecular sieve is widely used in petroleum refining and petrochemical industry as a good shape-selective catalyst, there is two-dimentional ten-ring pore passage structure, its composition silica alumina ratio can by 10 to total silicon, surface acidic strength and the advantages such as controllable that distribute, become and have the molecular sieve catalyst that height selects shape production light olefin.But micropore ZSM-5 molecular sieve is when relating to macromolecular reaction, because its duct is less, reactant molecule diffusion is hindered, and macromolecular reaction thing crystal duct extremely difficult to get access reacts or large molecular product diffuses out also more difficult from duct, thus limits its range of application.For catalytic reaction, for accelerating the diffusion of reactant molecule and product molecule, two kinds of measures can be taked: one is synthesizing small-grain molecular sieve, shortening the diffusion path of reactant and product.Two is apertures that post processing modification expands molecular sieve.But at present because small crystal grain molecular sieve easily sinters gathering in catalytic reaction process, and be separated comparatively difficulty, thus limit its application industrially.Post processing study on the modification is comparatively extensive, major part work mainly concentrates on steam or acid treatment dealuminzation, and to carry out alkali treatment to molecular sieve be a more novel processing method, passes through basic treatment, optionally deviating from framework silicon, is the microporous mesoporous a kind of effective method of preparation.And adopt mixed base process can retain microcellular structure to greatest extent while generation is mesoporous, and reduce the strong acid quantity of molecular sieve.Compared with inorganic base, the modification rate of organic base to molecular sieve is slower and gentle, has controllability, and can play the effect of duct growth regulator.In numerous after-treatment modification method, its treatment effect is obvious, simple to operate, does not need special installation, with low cost, has a extensive future.
The patent CN101428817A sodium hydroxide solution of 0.1 ~ 5mmol/L processes ZSM-5 molecular sieve 10 ~ 48h at 20 ~ 90 DEG C, and obtain the large aperture ZSM-5 zeolite that diameter is 160 ~ 190nm, its mesopore surface area reaches as high as 217m
2/ g, but microcellular structure is subject to very big destruction, and micropore specific surface only has 141.3m
2/ g.
Patent CN1530322A in 50 ~ 100 DEG C of process ZSM-51 ~ 7h, the highest obtains 250m with the aqueous slkali of 0.1 ~ 0.5mol/L
2the mesopore surface area of/g, but its microcellular structure is also the more serious of destruction.
Masaru Ogura etc. adopt the sodium hydroxide solution process ZSM-5 zeolite 5 ~ 300min of 0.05 ~ 0.2mol/L in Applied Catalysis A:General 219 (2001) 33 – 43, find that the ZSM-5 mesopore surface area of 0.2mol/L naoh treatment is by 6.6m
2/ g is increased to 115.4m
2/ g, micropore specific area is then from 296.4m
2/ g is reduced to 205m
2/ g.Although micropore specific area retains more, mesoporous content is also lower.
Barbara Gil etc. process ZSM-5 zeolite 1h with the sodium hydroxide solution of 0.1 ~ 1mol/L at 80 DEG C in Catalysis Today 152 (2010) 24 – 32, find that the ZSM-5 mesopore surface area of 0.5mol/L naoh treatment is by 67m
2/ g is increased to 211m
2/ g, micropore specific area is then from 288m
2/ g is reduced to 220m
2/ g, when concentration is increased to 1mol/L, micropore, mesopore surface area all decline more, and degree of crystallinity also sharply declines.
Johan C.Groen etc. adopts two step post treatment methods in Microporous and Mesoporous Materials87 (2005) 153 – 161, first at 65 DEG C, 30min is processed with 0.2mol/L NaOH, and then steam 873K process 5h, the sample mesopore surface area after process is by 40m
2/ g is increased to 230m
2/ g, micropore specific area is then from 390m
2/ g is reduced to 235m
2/ g.
Christian Fernandez etc. uses NaOH and hydrochloric acid soda acid mixed processing to prepare multi-stage porous ZSM-5 molecular sieve in Chem.Eur.J.16 (2010) 6224 – 6233.First adopt 0.2mol/L sodium hydroxide solution to process 30min at 65 DEG C, and then at 70 DEG C, process 6h by the hydrochloric acid solution of 0.1mol/L, the sample mesopore surface area after process is by 62m
2/ g is increased to 275m
2/ g, micropore specific area is then from 395m
2/ g is reduced to 298m
2/ g.
Sonia Abello etc. uses 1mol/L tetrapropyl oxyammonia (TPAOH) or tetrabutylammonium hydroxide amine (TBAOH) at 65 ~ 85 DEG C, process 0.5 ~ 8h in Applied Catalysis A:General364 (2009) 191 – 198, between finding when treated when 5h, mesopore surface area is by 60m
2/ g is increased to 180m
2/ g, starts to decline afterwards.And contrasting the NaOH process of 2mol/L, the NaOH of 2mol/L processes 30min at identical conditions, and mesopore surface area is by 60m
2/ g is increased to 277m
2/ g, but compared with organic amine process, inorganic base is comparatively large to the destructiveness of framework of molecular sieve, causes degree of crystallinity obviously to reduce.
Summary of the invention
The ZSM-5 molecular sieve used in catalyst of the present invention is for current technology, namely the simple inorganic base that uses destroys comparatively large to framework of molecular sieve and is difficult to control, simple use organic base cost is higher, the problems such as reaction rate is slower, invented one aim to provide higher mesopore surface area while retain microcellular structure to greatest extent, and alleviate the method for modifying of the destruction to framework of molecular sieve.
The method of modifying of the ZSM-5 molecular sieve used in catalyst of the present invention mainly comprises alkali treatment and acid treatment.Alkali treatment process uses organic base and the process of inorganic base mixed base, in conjunction with inorganic base treatment effect obviously and the mesoporous ZSM-5 that obtains of organic base process without the need to carrying out ammonium ion exchange again, and the speed of desiliconization is slower than conventional alkali treatment method, the advantages such as easy control, overcome the degree of crystallinity of inorganic base processing procedure Middle molecule sieve, acid amount, the difference such as heat endurance are larger, organic base processing cost is high, desiliconization selective poor, have a large amount of aluminium in process and be dissolved in the medium shortcoming of organic alkali solution, preparation ZSM-5 sample generate mesoporous while retain microcellular structure to greatest extent, and the destruction alleviated framework of molecular sieve, reduce the strong acid quantity of molecular sieve, acid treatment process is then remove the indefiniteness aluminium in zeolite crystal, thus reaches the object in dredging duct.
One of the present invention is mesoporous-micro porous molecular sieve hydrocracking catalyst preparation method.Catalyst composition comprises aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of ultra-low oxidized sodium, the USY molecular sieve of potassium oxide content and the composite modified ZSM-5 molecular sieve of one.Hydrocracking catalyst prepared by this method, can produce tail oil, heavy naphtha and diesel oil flexibly, and catalyst has tail oil and heavy naphtha total recovery is high, condensation point of diesel oil is low and tail oil BMCI value is low feature.
The method of modifying of the ZSM-5 molecular sieve used in catalyst, comprises the following steps:
(1) prepare the organic base Oh (Organic hydroxides) of variable concentrations and the mixed solution of inorganic base Inh (Inorganic hydroxides) (different Oh/Inh), keep total OH
-concentration is in (0.05 ~ 0.5mol/L) scope, and the value of Oh/Inh can change in 0.1 ~ 1 scope;
(2) get ZSM-5 zeolite, join in mixed ammonium/alkali solutions prepared by step (1) by the solid-to-liquid ratio of 10 ~ 100mL/g, at 25 ~ 95 DEG C, stir 10 ~ 420min;
(3) sample prepared by step (2) is carried out through frozen water sudden cold, filter, dry, roasting;
(4) sample that step (3) obtains is mixed according to a certain percentage with organic acid earth solution, at room temperature stir, then stir process 5 ~ 300min at 25 ~ 95 DEG C;
(5) product step (4) obtained after filtration, wash, be drying to obtain the modified ZSM-5 zeolite of process.
According to ZSM-5 method of modifying of the present invention, wherein step (1) described mixed base is the mixed solution of organic base tetramethyl oxyammonia (TMAOH) or hexamethylene diamine and inorganic base KOH or NaOH; Add the OH of aqueous slkali
-concentration is that 0.05 ~ 0.5mol/L, Oh/Inh molar ratio can change in 0.1 ~ 1 scope.
The solid-to-liquid ratio of step (2) described mixed ammonium/alkali solutions and ZSM-5 is 10 ~ 100mL/g, preferably 20 ~ 80mL/g; Treatment temperature is 25 ~ 95 DEG C, preferably 35 ~ 80 DEG C; Processing time is 10 ~ 480min, preferably 30 ~ 300min.
Organic acid earth solution described in step (4) is citric acid 0.001 ~ 0.1 interpolation lanthanum nitrate in molar ratio, and citric acid concentration is 0.05 ~ 1mol/L, and treatment temperature is 25 ~ 95 DEG C, preferably 35 ~ 80 DEG C; Processing time is 5 ~ 360min, preferably 1 ~ 4h.
The ZSM-5 zeolite of step (5) gained has following character: the XRD feature spectrogram with ZSM-5; At N
2there is micropore and mesoporous composite bore diameter in the aperture measured by adsorption-desorption, mesoporous high with micropore specific area.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the ZSM-5 modified zeolite that embodiment 1 obtains
Fig. 2 is the graph of pore diameter distribution of the ZSM-5 modified zeolite that embodiment 1 obtains
Detailed description of the invention
In the inventive method, the crystal structure of modified ZSM-5 zeolite sample adopts Rigaku D/max-2500 type X-ray diffractometer of science.Condition of work is: graphite monochromator, Cu K alpha ray (λ=0.154nm), tube current 40mA, tube voltage 40kV, and walk wide 0.02 °, sweep speed is 12 °/min, repeatable accuracy 1/1000 °.Wideangle scanning scope 3 °≤2 θ≤80 °.
The porous of sample, at Kang Ta instrument company of U.S. Quantachrome Instruments NOVA 2000e high speed specific surface and lacunarity analysis instrument, carries out nitrogen adsorption/detachment assays under 77K liquid nitrogen temperature, image data point.Before test, all samples is Fruit storage 5-10 hour at 200 DEG C all; The calculating of specific surface is obtained by multiple spot BET theory calculate, coefficient correlation (Correlation Cofficient) >0.9999; Pore-size distribution adopts Barret-Joyner-Halenda (BJH) method or Density function Theory(DFT) calculate, the pore passage structure of sample is also analyzed by the theory of being correlated with.
Give detailed description below by specific embodiment to the ZSM-5 molecular sieve method of modifying used in invention and method for preparing catalyst, but be not limited to embodiment.
The raw material ZSM-5 that the present invention uses is from Shenneng Science-Technology Co., Ltd., Tianjin, and its silica alumina ratio is 38, and specific area is 364m
2/ g, micropore specific area 277m
2/ g, mesopore surface area 87m
2/ g.The acid used, alkali and solvent are analyzes pure chemistry reagent.
Embodiment 1
Get TMAOH and the KOH (TMA that 1g ZSM-5 zeolite adds 50mL 0.2mol/L
+/ OH
-=6) in, 2h is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-1.
As seen from Figure 1, BA-1 sample has the XRD feature spectrogram of ZSM-5, still keeps that good ZSM-5's is zeolite structured.As seen from Figure 2, after modification, exist significantly mesoporous in ZSM-5 zeolite, aperture is concentrated, and most probable pore size is 3.84nm.
Embodiment 2
Get TMAOH and the NaOH (TMA that 1g ZSM-5 zeolite adds 50mL0.2mol/L
+/ OH
-=6) in, 30min is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-2.
Embodiment 3
Get TMAOH and the KOH (TMA that 1g ZSM-5 zeolite adds 50mL0.2mol/L
+/ OH
-=2) in, 300min is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-3.
Embodiment 4
Get hexamethylene diamine and KOH (hexamethylene diamine/OH that 1g ZSM-5 zeolite adds 50mL0.2mol/L
-=6) in, 2h is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-4.
Embodiment 5
Get hexamethylene diamine and NaOH (hexamethylene diamine/OH that 1g ZSM-5 zeolite adds 50mL 0.2mol/L
-=6) in, 2h is stirred at 65 DEG C, sudden cold by frozen water, filter, deionized water washing is to neutral, and gained solid is dried at 110 DEG C, is placed in Muffle furnace 550 DEG C of roasting 5h, by the HZSM-5 molecular sieve 80 DEG C of process 2h in the citric acid and lanthanum nitrate hexahydrate of 0.01mol/L obtained, gained sample number into spectrum is BA-5.
Comparative example 1
Getting 1g ZSM-5 zeolite adds in the NaOH of 50mL 0.2mol/L, stirs 4h at 80 DEG C, filters, and deionized water washing is to neutral, and it is BA-6 that gained solid dries gained sample number into spectrum at 110 DEG C.
Comparative example 2
Get 1g ZSM-5 zeolite and add 80 DEG C of process 4h in the citric acid solution of 50mL 0.20mol/L, filtration, deionized water washing are to neutral, and it is BA-7 that gained solid dries gained sample number into spectrum at 110 DEG C.
Comparative example 3
Getting 1g ZSM-5 zeolite adds in the TMAOH of 50mL 0.2mol/L, stirs 5h at 65 DEG C, filters, and deionized water washing is to neutral, and gained solid is dried at 110 DEG C, and gained sample number into spectrum is BA-8.
The pore structure character of embodiment 1 ~ 5 and the ZSM-5 modified zeolite sample prepared by comparative example 1 ~ 3 lists in table 1.The pore structure character of sample involved by table 1 embodiment and comparative example
Embodiment 5
35g USY molecular sieve, 5g modified zsm-5 zeolite (BA-1), 40g macroporous aluminium oxide, 20 little porous aluminum oxides and 5.2g sesbania powder are put into roller, mixed grind 30min, the mixed solution of 10g red fuming nitric acid (RFNA) and 100g water is added after mixing, be extruded into the cylindrical bar of 1.5mm, 120 DEG C of dry 4hr, in 550 DEG C of air atmospheres, roasting 5hr obtains catalyst carrier.The solution room temperature immersion 1hr of 100ml water is dissolved in again, 120 DEG C of dry 4hr, roasting 5hr in 500 DEG C of air atmospheres, obtained hydrocracking catalyst of the present invention with 44g nickel nitrate, 79g ammonium metatungstate.
Comparative example 4
Comparative example 4 catalyst is commercially available similar catalyst.Main component contains Y molecular sieve, amorphous aluminum silicide and alumina composition etc. by analysis, and metal component is tungsten and nickel.
Table 2 feedstock property
Table 3 catalyst 200ml hydrogenation plant evaluating data
| Catalyst | Embodiment 5 | Comparative example 4 |
| Feedstock oil | VGO+CGO | VGO+CGO |
| Volume space velocity during liquid, h -1 | 2.5 | 2.5 |
| Hydrogen to oil volume ratio | 800:1 | 800:1 |
| Reaction pressure, MPa | 9.0 | 9.0 |
| Reaction temperature, DEG C | 383 | 384 |
| Product yield, wt.% | 98.6 | 98.6 |
| Light naphthar HK ~ 65 DEG C | 3.33 | 5.03 |
| Heavy naphtha 65 DEG C ~ 165 DEG C | 25.77 | 20.07 |
| Diesel oil 165 DEG C ~ 350 DEG C | 34.70 | 37.76 |
| Condensation point of diesel oil, DEG C | <-45 | -16 |
| Tail oil > 350 DEG C | 37.20 | 37.14 |
| BMCI value | 7 | 12 |
As can be seen from Table 3, the tail oil in embodiment 5 and heavy naphtha yield are all higher than comparative example 4, and condensation point of diesel oil and tail oil BMCI value are all better than comparative example 4.Catalyst has tail oil and heavy naphtha total recovery is high, condensation point of diesel oil is low and tail oil BMCI value is low feature.
Claims (3)
1. mesoporous-micro porous molecular sieve hydrocracking catalyst, catalyst composition comprises aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of ultra-low oxidized sodium, the USY molecular sieve of potassium oxide content and a kind of modified zsm-5 zeolite; It is characterized in that: described USY molecular sieve sodium oxide molybdena and potassium oxide total content are 0.01 ~ 0.03wt.%; Described ZSM-5 molecular sieve is through following composite modifying method modification:
(1) prepare the organic base of variable concentrations and the mixed solution of inorganic base, keep total OH
-concentration is in the scope of 0.05 ~ 0.5mol/L, and the molar ratio of organic base/inorganic base changes in 0.1 ~ 1 scope;
(2) get ZSM-5 zeolite, join in mixed ammonium/alkali solutions prepared by step (1) by the solid-to-liquid ratio of 10 ~ 100ml/g, at 25 ~ 95 DEG C, stir 10 ~ 480min;
(3) sample prepared by step (2) is carried out through frozen water sudden cold, filter, dry, roasting;
(4) sample that step (3) obtains is mixed with organic acid earth solution, at room temperature stir, then stir process 5 ~ 360min at 25 ~ 95 DEG C; Described organic acid earth solution is citric acid 0.001 ~ 0.1 interpolation lanthanum nitrate in molar ratio, and citric acid is 0.05 ~ 1mol/L;
(5) product step (4) obtained after filtration, wash, be drying to obtain the modified ZSM-5 zeolite of process.
2. according to according to claim 1 mesoporous-micro porous molecular sieve hydrocracking catalyst, it is characterized in that: step (1) described mixed base is the mixed solution of organic base and inorganic base, wherein organic base is tetramethyl oxyammonia or hexamethylene diamine, and inorganic base is KOH or NaOH.
3. according to according to claim 1 mesoporous-micro porous molecular sieve hydrocracking catalyst, it is characterized in that: the organic acid earth solution described in step (4) is the mixed solution of citric acid and lanthanum nitrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271289A (en) * | 2015-11-02 | 2016-01-27 | 太原理工大学 | Method for directionally removing amorphous silicon aluminum species in nanocrystalline accumulation clearance of EU-1 molecular sieve |
| CN106669807A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of catalyst for improving viscosity index of hydrocracking tail oil |
| CN106669803A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Catalyst applied to production of high-viscosity index hydrocracking tail oil and preparation method thereof |
| CN106669812A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst for producing low-condensation-point tail oil and preparation method thereof |
| CN106669806A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Catalyst for producing low-freezing point diesel oil, and preparation method thereof |
| CN106669800A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrocracking catalyst for reducing straight chain alkanes in tail oil, and preparation method thereof |
| CN106669801A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Catalyst for producing hydrocracking tail oil with low content of straight chain alkanes, and preparation method thereof |
| CN106669799A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst for maximum-yield production of low freezing point diesel fuel |
| CN107344104A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst for producing high-quality ethylene raw material and its preparation method and application |
| CN111375441A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Multistage hole HZSM-5 molecular sieve |
| CN112978750A (en) * | 2021-01-26 | 2021-06-18 | 青岛科技大学 | Molecular sieve modification post-treatment method |
| CN114522722A (en) * | 2022-02-25 | 2022-05-24 | 中国地质科学院矿产综合利用研究所 | Rare earth mesoporous molecular sieve, preparation method thereof and catalyst containing molecular sieve |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6069106A (en) * | 1994-03-03 | 2000-05-30 | Hettinger, Jr.; William P | Process and compositions for Mn containing catalyst for carbo-metallic hydrocarbons |
| CN1335360A (en) * | 2001-09-11 | 2002-02-13 | 中国石油天然气股份有限公司 | Method and catalyst for selective hydrogenation refining of cracked gasoline |
| CN1552808A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing screening sieve and fluorine, preparing method thereof |
| CN1727447A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Hydrogenant cracking catalyst of containing zeolite, and preparation method |
| CN103059973A (en) * | 2011-10-24 | 2013-04-24 | 中国科学院过程工程研究所 | Coal tar full-fraction hydrogenation method for coupling slurry bed and static bed |
-
2013
- 2013-11-15 CN CN201310574627.3A patent/CN104624227A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6069106A (en) * | 1994-03-03 | 2000-05-30 | Hettinger, Jr.; William P | Process and compositions for Mn containing catalyst for carbo-metallic hydrocarbons |
| CN1335360A (en) * | 2001-09-11 | 2002-02-13 | 中国石油天然气股份有限公司 | Method and catalyst for selective hydrogenation refining of cracked gasoline |
| CN1552808A (en) * | 2003-05-30 | 2004-12-08 | 中国石油化工股份有限公司 | Catalytic cracking catalyst containing screening sieve and fluorine, preparing method thereof |
| CN1727447A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Hydrogenant cracking catalyst of containing zeolite, and preparation method |
| CN103059973A (en) * | 2011-10-24 | 2013-04-24 | 中国科学院过程工程研究所 | Coal tar full-fraction hydrogenation method for coupling slurry bed and static bed |
Non-Patent Citations (1)
| Title |
|---|
| 李莎 等: "TPAOH/NaOH混合碱体系对ZSM-5沸石的改性及其催化性能研究", 《燃料化学学报》 * |
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