CN1667093A - High performance hydrocracking catalyst and process for preparing same - Google Patents
High performance hydrocracking catalyst and process for preparing same Download PDFInfo
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- CN1667093A CN1667093A CN 200510200094 CN200510200094A CN1667093A CN 1667093 A CN1667093 A CN 1667093A CN 200510200094 CN200510200094 CN 200510200094 CN 200510200094 A CN200510200094 A CN 200510200094A CN 1667093 A CN1667093 A CN 1667093A
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- molecular sieve
- hydrocracking
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- zeolite
- complex carrier
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Abstract
This invention is one kind of high capability hydrogenation cracking catalyst and its preparing method, it belongs to new material, oil refining, petrochemical industry and energy technique field. Metal active component is carried by complex carrier, the catalyst prepared not only has high hydrocracking activity, but also high hydrodesulfurization activity, it can be use to deeply remove sulfur and nitrogen and other mixed atoms when in ifp basf hydrocracking process of lightening heavy oil fraction. Complex carrier is generated by interpose hole molecular sieve and zeolite molecular sieve. The central hole of complex carrier is propitious to highly disperse of active metal and reduce inside diffusional resistance of reactant molecule, and hydrogenation center and cracking center can be provided by acidity of zeolite molecular sieve. The beneficial effect of this invention is that dibenzanthracene thiophene and its derivant can fully transformed, cracked product in products can almost more than 80%. It is mainly used in lightening of heavy oil fraction in oil and coal liquid processing, sulfur, nitrogen and other mixed atoms can be removed at the same time.
Description
Technical field
The invention belongs to novel material, refining of petroleum, petrochemical complex and energy technology field.
Background technology
Hydrocracking is one of deep-processing process of oil and coal liquid, faces in the nitrogen atmosphere heavy distillate to be cracked into light ends oil under the effect of catalyzer.Hydrogenation process is carried out under higher temperature usually, and general energy consumption is very high, and this process need consume the hydrogen of a large amount of costlinesses.Thereby, objectively require hydrocracking process to unite two into one by the hydrofining technology close with reaction conditions, when making the heavy oil lighting, remove heteroatomss such as wherein sulphur, nitrogen, to produce clean fuel and high-quality industrial chemicals
Traditional hydrocracking catalyst is to support the dual-function catalyst that Co (Ni)-Mo or Ni-W bimetal sulfide are made with the complex carrier that contains Y zeolite and aluminum oxide, and it is with hydrogenation and cracking function.Because the composition of catalyzer is similar to Hydrobon catalyst, this catalyzer also has certain hydrodesulfurization activity.But the hydrodesulfurization activity of traditional hydrocracking catalyst is all lower, is difficult to realize in same reactor simultaneously hydrocracking and hydrofining reaction.
It is generally acknowledged that the hydrodesulfurization activity of catalyzer is relevant with the dispersity of metal component, the high more hydrodesulfurization reaction activity of dispersity is high more.And the specific surface area of dispersity and catalyzer and pore volume are closely related, so the ideal carrier should have very high specific surface area.The scientist of U.S. Mobil company successfully synthesized a series of mesopore molecular sieves such as MCM-41 in 1992.With MCM-41 is example, and its aperture is adjustable between 1.5-10nm, and has very big surface-area (＞1000m
2/ g) with than large pore volume, be a kind of ideal hydrodesulfurization catalyst support.We have gone out the active Hydrobon catalyst (ZL00101265.7) of making carrier far above aluminum oxide with mesopore molecular sieve MCM-41 as preparing carriers.But, the acidity of mesopore molecular sieve a little less than, do not have very high hydrogenation cracking activity.As if the aluminum oxide that replaces with mesopore molecular sieve in traditional carrier of hydrocracking catalyst, then can make a kind of polyfunctional catalyst with hydrogenation, cracking and desulfurization/denitrification activity, hydrocracking and unifining process might be united two into one.
Summary of the invention
The purpose of this invention is to provide and a kind ofly support high-performance catalyst for hydrocracking of transition metal and preparation method thereof with mesopore-micropore complex carrier.
Technical solution of the present invention is, a kind of high-performance catalyst for hydrocracking adopts mesopore-microvoid structure complex carrier, its composition: by mass percentage, and mesoporous molecular sieve 0-100%, zeolite molecular sieve 0-100%; Metal active constituent is Ni-Mo, Co-Mo, Ni-W, Co-W, Pt, Pd or Ru; The per-cent that the loading of metal component accounts for the catalyzer total mass is 0-35%.
Its carrier of a kind of high-activity hydrofining catalyst is mesopore-micropore complex carrier, its composition: by mass percentage, and mesopore molecular sieve 25-75%, zeolite molecular sieve 25-75%.
Carrier mesolite molecular sieve is y-type zeolite, A type zeolite, X type zeolite, zeolite beta, ZSM-5 type zeolite or the mordenite molecular sieve with microchannel structure, and their hydrogen type molecular sieves of making through proton exchange.
Mesopore molecular sieve is MCM-41, MCM-48, SBA-15 or the SBA-16 molecular sieve with central hole structure in the carrier.
A kind of high-activity hydrofining catalyst by mass percentage, contains Ni (Co) 0～15% in the catalyzer, Mo (W) 5-35%; Contain Pt, Pd or Ru 0-10% in the catalyzer.
In molar ratio, catalyst n i (Co)/Mo (W) is than being 0-1.0.
In molar ratio, catalyst n i (Co)/Mo (W) is than being 0.75.
The method for preparing a kind of high performance hydrocracking controlling catalyst:
A. zeolite molecular sieve powder and mesoporous molecular sieve powder mixes is even, make micropore-mesopore complex carrier;
B. complex carrier is joined in the aqueous solution that contains metal-salt, dipping is 0.5-2 hour under agitation condition, then at 80-160 ℃ of dry 2-20 hour, evaporating water, 400-600 ℃ in air roasting 2-10 hour, make oxidized catalyst;
C. sulfidation: load oxidized catalyst in the fixed-bed reactor, feed 5-20%H
2S/H
2Vulcanizing agent, and keep 0-1.0MPa pressure, the adjustments of gas flow is 20-200ml/g.min; In 0.5-2 hour reactor is warming up to 200-600 ℃ from 15-25 ℃ then, sulfuration is 1-8 hour under this temperature.
Carrying metal adopts equi-volume impregnating, dry type kneading method, excessive pickling process or vacuum impregnation technology, preferably vacuum impregnation technology.
The lighting that this catalyzer is used for various heavy distillates removes heteroatomss such as sulphur nitrogen simultaneously, is specially adapted to the degree of depth and the refining processing of fraction oil of petroleum and coal liquid.
The forming method of this catalyzer adopts and drips ball forming, spin granulation, extrusion molding, compression molding etc., is best to drip ball forming and extrusion molding.Catalyst shape can be sphere, bar shaped, sheet type or particulate state, and that bar shaped comprises is cylindrical, trilobal, quatrefoil etc., with spherical and bar shaped for well.
The beneficial effect that the present invention reached is, dibenzothiophene and derivative thereof almost all transform, and split product accounts for more than 80% in the product.
Embodiment
Example 1
This example is the preparation method of the Ni-Mo hydrocracking catalyst that supports of complex carrier.
Mechanical mixing is adopted in the preparation of complex carrier.Place mortar to grind 30 minutes 1 gram Hydrogen Y zeolite and 3 gram MCM-41 mesopore molecular sieves, make mixed uniformly complex carrier.
The catalyst activity component support the employing co-impregnation.Take by weighing 1.19 gram Ammonium Heptamolybdate ((NH
4)
6Mo
7O
244H
2O) and 1.26 gram nickelous nitrate (Ni (NO
3)
26H
2O) be dissolved in 50 ml deionized water, make dipping solution.Take by weighing 3 gram complex carriers, add in the dipping solution that has prepared, flooded 1 hour in room temperature.Quick evaporating water, 120 ℃ of dryings 12 hours, roasting 5 hours in air under 450 ℃ then obtained the Ni-Mo catalyst precursor that complex carrier supports.MoO
3Loading is 20% (quality), and the loading of NiO is 7.8% (quality).
Example 2
This example is hydrogenating desulfurization and the hydrogenation cracking activity evaluation method and the result of catalyzer of the present invention.
Hydrodesulfurization reaction carries out on stainless steel high pressure fixed bed device.Raw material is the perhydronaphthalene solution that contains the dibenzothiophene of 0.8wt%.Appreciation condition: temperature of reaction is 300 ℃; Stagnation pressure is 5MPa; H
2/ solid-liquid ratio is 1600Nm
3/ m
3The liquid air speed is 27h
-1The Agilent6890 gas chromatographic analysis of raw material and product, hydrodesulfurization activity represent that with the transformation efficiency of dibenzothiophene hydrogenation cracking activity is described with benzene and hexanaphthene overall selectivity.
The transformation efficiency of dibenzothiophene illustrates that greater than 99% this catalyzer has very high low temperature hydrogenation desulphurization reaction activity under this reaction conditions.The overall selectivity of benzene and hexanaphthene is higher than 80% in the hydrogenating desulfurization product, and the cracking activity when making carrier with HY is suitable, shows that this catalyzer also has very high hydrogenation cracking activity.The prepared target catalyzer of this explanation is a kind of hydrocracking catalyst with very high hydrodesulfurization activity.
Claims (10)
1. a high-performance catalyst for hydrocracking is characterized in that, adopts the complex carrier with mesopore-micropore stepped pore distribution structure, and its carrier is formed: by mass percentage, and mesoporous molecular sieve 0-100%, zeolite molecular sieve 0-100%; Metal active constituent is Ni-Mo, Co-Mo, Ni-W, Co-W, Pt, Pd or Ru; The per-cent that the charge capacity of metal active constituent accounts for the catalyzer total mass is 0-35%.
2. a kind of high-performance catalyst for hydrocracking according to claim 1, it is characterized in that, its carrier is to mix the porous material of the stepped pore distribution structure that obtains by mesoporous molecular sieve and zeolite molecular sieve, it is formed by mass percentage, mesoporous molecular sieve 25-75%, zeolite molecular sieve 25-75%.
3. a kind of high-performance catalyst for hydrocracking according to claim 1 and 2, it is characterized in that the zeolite molecular sieve in the complex carrier is the hydrogen type molecular sieve that y-type zeolite, A type zeolite, X type zeolite, zeolite beta, ZSM-5 type zeolite or mordenite molecular sieve with microchannel structure and they make through proton exchange.
4. a kind of high-performance catalyst for hydrocracking according to claim 1 and 2 is characterized in that, the mesoporous molecular sieve in the complex carrier is MCM-41, MCM-48, SBA-15 or the SBA-16 molecular sieve with central hole structure.
5. a kind of high-performance catalyst for hydrocracking according to claim 1 is characterized in that, by mass percentage, contains Ni (Co) 0-15% in the catalyzer, Mo (W) 5-35%; Contain Pt, Pd or Ru 0-10% in the catalyzer.
6. a kind of according to claim 1 or 5 high-performance catalyst for hydrocracking is characterized in that, in molar ratio, catalyst n i (Co)/Mo (W) is than being 0-1.0.
7. prepare the method for the described a kind of high-performance catalyst for hydrocracking of claim 1, it is characterized in that, its preparation process is as follows:
A. zeolite molecular sieve powder and mesoporous molecular sieve powder mixes is even, make micropore-mesopore complex carrier;
B. complex carrier is joined in the metal salt solution that contains metal active constituent, dipping is 0.5-2 hour under agitation condition, then at 80-160 ℃ of dry 2-20 hour, and evaporating water, 400-600 ℃ in air roasting 2-10 hour, make oxidized catalyst;
C. sulfidation: load oxidized catalyst in the fixed-bed reactor, feed the vulcanizing agent of 5-20% H2S/H2, and keep 0-1.0MPa pressure, the adjustments of gas flow is 20-200ml/g.min; In 0.5-2 hour reactor is warming up to 200-600 ℃ from 15-25 ℃ then, sulfuration is 1-8 hour under this temperature.
8. the preparation method of a kind of high-performance catalyst for hydrocracking according to claim 7 is characterized in that, moulding is adopted and dripped ball, extrusion method.
9. the preparation method of a kind of high-performance catalyst for hydrocracking according to claim 7 is characterized in that, carrying metal adopts equi-volume impregnating, dry type kneading method, excessive pickling process or vacuum impregnation technology.
10. according to the purposes of a kind of high-performance catalyst for hydrocracking of the described preparation of claim 7, it is characterized in that, this catalyzer is used for the hydrocracking process process of heavy distillate, when heavy oil fraction is cracked into light ends oil, remove heteroatomss such as wherein sulphur, nitrogen, to produce clean fuel or high-quality industrial chemicals; Be specially adapted to the deep processing of fraction oil of petroleum and coal liquid.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011047528A1 (en) * | 2009-10-22 | 2011-04-28 | 中国石油天然气股份有限公司 | Bi-microporous-mesoporous composite molecular sieve y-beta/ mcm-41 and preparing method thereof |
| WO2013152577A1 (en) * | 2012-04-09 | 2013-10-17 | 温州大学 | Novel high activity hydrogen desulfurization catalyst and preparation method thereof |
| CN104874417A (en) * | 2014-02-28 | 2015-09-02 | 中国科学院青岛生物能源与过程研究所 | Composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
| CN105126899A (en) * | 2015-07-16 | 2015-12-09 | 福州大学 | Poor-quality heavy oil suspended bed hydrogenation catalyst supported on molecular sieve, preparation method and use method thereof |
| CN105435831A (en) * | 2015-11-12 | 2016-03-30 | 北京华石联合能源科技发展有限公司 | Microspherical catalyst as well as preparation method and application thereof |
| 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 |
| CN108473879A (en) * | 2016-02-25 | 2018-08-31 | 沙特基础工业全球技术有限公司 | Unionfining desulfurization for heavy hydrocarbon and the method that is hydrocracked |
| US10822552B2 (en) | 2016-03-01 | 2020-11-03 | Sabic Global Technologies B.V. | Process for producing monoaromatic hydrocarbons from a hydrocarbon feed comprising polyaromatics |
-
2005
- 2005-02-22 CN CN 200510200094 patent/CN1667093A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011047528A1 (en) * | 2009-10-22 | 2011-04-28 | 中国石油天然气股份有限公司 | Bi-microporous-mesoporous composite molecular sieve y-beta/ mcm-41 and preparing method thereof |
| WO2013152577A1 (en) * | 2012-04-09 | 2013-10-17 | 温州大学 | Novel high activity hydrogen desulfurization catalyst and preparation method thereof |
| CN104874417A (en) * | 2014-02-28 | 2015-09-02 | 中国科学院青岛生物能源与过程研究所 | Composite carrier-supported cobalt-based Fischer-Tropsch synthesis catalyst, and preparation method and application thereof |
| CN105126899A (en) * | 2015-07-16 | 2015-12-09 | 福州大学 | Poor-quality heavy oil suspended bed hydrogenation catalyst supported on molecular sieve, preparation method and use method thereof |
| CN105126899B (en) * | 2015-07-16 | 2017-12-29 | 福州大学 | A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application |
| 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 |
| CN106669807B (en) * | 2015-11-09 | 2019-09-10 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst improving hydrocracking tail oil viscosity index (VI) |
| CN105435831A (en) * | 2015-11-12 | 2016-03-30 | 北京华石联合能源科技发展有限公司 | Microspherical catalyst as well as preparation method and application thereof |
| CN108473879A (en) * | 2016-02-25 | 2018-08-31 | 沙特基础工业全球技术有限公司 | Unionfining desulfurization for heavy hydrocarbon and the method that is hydrocracked |
| US11001765B2 (en) | 2016-02-25 | 2021-05-11 | Sabic Global Technologies B.V. | Process for combined hydrodesulfurization and hydrocracking of heavy hydrocarbons |
| US10822552B2 (en) | 2016-03-01 | 2020-11-03 | Sabic Global Technologies B.V. | Process for producing monoaromatic hydrocarbons from a hydrocarbon feed comprising polyaromatics |
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