CN109847793A - A kind of method of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst - Google Patents
A kind of method of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst Download PDFInfo
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Abstract
Non-supported hydrogenation catalyst is difficult to introduce acidic components, the present invention provides a kind of methods of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst due to not having carrier.A kind of ZSM-5 molecular sieve nano-cluster solution with nanoscale is synthesized first, it is then introduced into the bimetallic NiMo composite oxides suspension with layer structure, in acid ZSM-5 molecular sieve component intercalated layered metal composite oxide presoma, will be obtained by hydro-thermal eutectic technology has certain acid difunctional non-supported hydrogenation catalyst.The specific surface area of ZSM-5 molecular sieve base unsupported catalyst, Kong Rong and aperture prepared by the present invention all improve a lot, and compared to simple unsupported catalyst, modified unsupported catalyst has higher plus hydrogen open loop activity.
Description
Technical field
The present invention relates to a kind of preparation methods of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst.Tool
It says to body, the present invention relates to a kind of unsupported catalyst and preparation method thereof with ZSM-5 molecular sieve ingredient.
Background technique
Today's society, world industry are just developed with swift and violent speed, blood of the petroleum as industry, in socio-economic development
In play irreplaceable role, this has speeded up the exploitation paces of petroleum so that in the market the quality of petroleum worse and worse,
The content of sulphur nitrogen, the impurity such as polycyclic aromatic hydrocarbon is higher and higher, if these crude oil processing raw material as oil and gasoline, it will very
Big degree reduces the quality of product, so that containing a large amount of impurities in diesel oil, such as macromolecule sulphur, nitrogen compound and polycyclic virtue
Hydrocarbon, these substance combustions can generate a large amount of pollution gas, seriously pollute the environment that we depend on for existence, damage our body
Body health.
Under the situation of this sternness, exploitation high-performance hydrogenation catalyst is that very crucial, traditional hydrodesulfurization is urged
Agent is mainly loaded catalyst, due to the price of its material benefit, preferably plus hydrogen effect, receives extensive favor, but by
Largely limit that its is desulphurizing activated in the load capacity of active component, thus desulfurization effect further increase it is relatively difficult, because
This, unsupported catalyst initially entered among industrial production, in Exxon Mobil, Akzo Nobel and Nippon in 2001
Tri- company's joint development of Ketjen a kind of unsupported catalyst, carrier-free are that loaded catalyst and non-loading type are urged
The most important difference of agent, this Hydrobon catalyst are mainly made of active component, and active metal intensity is higher, because
This shows catalytic activity more higher than loaded catalyst.But the shortcomings that unsupported catalyst, also emerges in production,
It is acid weaker to be mainly reflected in it, intensity is not high, and specific surface area is relatively low, and active component is easy aggregation etc., so industry now
The application of production is not yet mature, and these problems letter is to be solved.
If further increasing its cracking performance on the basis of non-supported hydrogenation catalyst higher hydrogenation activity, so that
Aromatic hydrocarbons carries out appropriate cracking while adding hydrogen, this will generate more cycloalkane for having side chain, this is for diesel oil 16
The raising of alkane value has critically important value, it is desirable to realize this target, it is necessary to non-supported hydrogenation catalyst is modified,
To improve its acidity, and then improve its cracking performance.
Have disclosed in Chinese patent CN200810117102.6, CN200710012770.8, CN00109747.4 etc. and adds
The catalyst of hydrogen cracking function is carried on hydrogenation active component on the carriers such as molecular sieve, aluminium oxide, or by hydrogenation activity
Component and molecular sieve mechanical mixture are to assign its acidity, but these methods are often lower by load capacity, acid uneven, carry
The limitation of body opening road blocking etc., cannot obtain preferable effect.Also research introduces hydrogenation activity in sieve synthesis procedure
Component, but this method is not easy to form hydrogenation activity phase, cannot still reach and preferably add hydrogen effect.So using mode appropriate
Acidity, which is introduced into unsupported catalyst, to be particularly important.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of eutectic method synthesis ZSM-5 molecular sieve base is unsupported
The preparation method of type hydrogenation catalyst adds to reach in non-loading type so that two kinds of ingredients sufficiently combine in crystallization process
The purpose of proper sourness is assigned in hydrogen catalyst.
Present invention research synthesizes a kind of bimetal composite oxide with layer structure, will be located by hydrothermal crystallizing technology
It is embedded into layered mixed oxide presoma in the ZSM-5 molecular sieve nano-cluster of nanoscale, so that is finally prepared is non-negative
The existing stronger hydrogenation activity of supported catalyst has acidity appropriate again.
Specific preparation process is as follows for catalyst of the present invention:
(1) presoma of ZSM-5 molecular sieve is synthesized first in alkali free metal ion system.Chemical meter is taken by a certain percentage
Suitable aluminium isopropoxide is added afterwards, is slowly added into positive silicon after stirring clarification in beaker for the tetrapropylammonium hydroxide (TPAOH) of amount
Sour tetra-ethyl ester (TEOS) and deionized water continue to stir certain time, so that mixture is become clarification again, obtain ZSM-5 molecular sieve
Presoma stoste is fitted into crystallizing kettle by presoma stoste, and 90~180 DEG C obtain ZSM-5 molecular sieve nanometer in crystallization 2~10 hours
Cluster.
(2) ammonium molybdate, nickel nitrate are added to three mouthfuls containing deionized water in the ratio that nickel molybdenum molar ratio is 1~2:1
In flask, stirring and heating makes mixture become clarification, and ammonium hydroxide is added when reaching 90~100 DEG C in temperature, when solution becomes clarification again
When stop being added dropwise, solution is stirred to react 2~20 hours at 90~100 DEG C of constant temperature, obtains non-loading type NiMo catalyst precursor
Suspension.
(3) it takes a certain amount of ZSM-5 molecular sieve nano-cluster to mix with non-loading type NiMo catalyst precursor suspension, stirs
It mixes 5~10 hours, is packed into crystallizing kettle, taken out within crystallization 10~24 hours for 90~180 DEG C under stirring, filtering, washing, product
It is 10~24 hours dry at 60~100 DEG C, obtain ZSM-5 molecular sieve base non-loading type NiMo catalyst precursor powder.
(4) catalyst precursor powder can be formed using conventional forming method, such as tabletting, extrusion etc.,
300~550 DEG C roast 3~5 hours, obtain ZSM-5 molecular sieve base non-loading type NiMo catalyst.
The molar ratio of material of synthesis of molecular sieve presoma stoste of the present invention are as follows: 1.0SiO2: 0.003~0.005Al2O3:
0.45~0.5TPAOH:30~40H2O.There is acid non-supported hydrogenation catalyst prepared by the present invention, can be used for
The hydrofinishing of petroleum distillate, aromatic hydrocarbons etc. and plus hydrogen ring-opening reaction.Below by embodiment the present invention is further explained method:
Detailed description of the invention
Infrared (Py-IR) spectrogram of pyridine of ZSM-5 molecular sieve base non-supported hydrogenation catalyst prepared by Fig. 1 present invention.
The NH of ZSM-5 molecular sieve base non-supported hydrogenation catalyst prepared by Fig. 2 present invention3- TPD figure.
Specific embodiment:
Comparative example
Weigh 43.62 grams of nickel nitrates and 17.66 grams of ammonium molybdates dissolve respectively after be added sequentially in three-necked flask, stirring is simultaneously
Heating makes mixture become clarification, and ammonium hydroxide is slowly added into when temperature reaches 93 DEG C, and solution becomes cloudy first, continues that ammonium hydroxide change is added dropwise
Stopping being added dropwise when clarification, solution reacts the unsupported catalyst presoma suspension for obtaining green for 10 hours at 93 DEG C later,
Product obtains non-loading type NiMo catalyst precursor powder for 12 hours by filtering, washing, 100 DEG C of dryings.Precursor powder
It is formed by the way of tabletting, is roasted 4 hours at 350 DEG C, obtain non-loading type NiMo catalyst, be designated as Cat-0.
Embodiment 1
45.76 grams of tetrapropylammonium hydroxide (TPAOH) are weighed in beaker, the rear aluminium isopropoxide for being added 0.42 gram, stirring
42.52 grams of tetraethyl orthosilicates (TEOS) and 97.70 grams of deionized waters are slowly added dropwise after clarification, continues to stir, makes mixture again
Secondary change clarification, obtains ZSM-5 molecular sieve presoma stoste, ZSM-5 molecular sieve presoma stoste 160 DEG C of crystallization 3 in crystallizing kettle
It is taken out after hour, obtains ZSM-5 molecular sieve nano-cluster solution A.
Weigh 43.62 grams of nickel nitrates and 17.66 grams of ammonium molybdates dissolve respectively after be added sequentially in three-necked flask, stirring is simultaneously
Heating makes mixture become clarification, and ammonium hydroxide is slowly added into when temperature reaches 93 DEG C, and solution becomes cloudy first, continues that ammonium hydroxide change is added dropwise
Stop being added dropwise when clarification, solution reacts the unsupported catalyst presoma suspension B for obtaining green for 10 hours at 93 DEG C later.
It takes 60mL (butt is 4 grams) solution A in beaker, 107mL (butt is 6.0 grams) B is mixed with, is obtained later
Mixture C, mixture C are packed into crystallizing kettle after stirring 6 hours, take out within crystallization 12 hours for 160 DEG C under stirring, product exists
100 DEG C drying 12 hours, obtain modified non-loading type NiMo catalyst precursor powder.Precursor powder is using tabletting
Mode forms, and roasts 4 hours at 350 DEG C, obtains non-loading type NiMo catalyst, be designated as Cat-1.
Embodiment 2
45.76 grams of tetrapropylammonium hydroxide (TPAOH) are weighed in beaker, the rear aluminium isopropoxide for being added 0.42 gram, stirring
42.52 grams of tetraethyl orthosilicates (TEOS) and 97.70 grams of deionized waters are slowly added dropwise after clarification, continues to stir, makes mixture again
Secondary change clarification, obtains ZSM-5 molecular sieve presoma stoste, ZSM-5 molecular sieve presoma stoste 160 DEG C of crystallization 3 in crystallizing kettle
It is taken out after hour, obtains ZSM-5 molecular sieve nano-cluster solution A.
Weigh 43.62 grams of nickel nitrates and 17.66 grams of ammonium molybdates dissolve respectively after be added sequentially in three-necked flask, stirring is simultaneously
Heating makes mixture become clarification, and ammonium hydroxide is slowly added into when temperature reaches 93 DEG C, and solution becomes cloudy first, continues that ammonium hydroxide change is added dropwise
Stop being added dropwise when clarification, solution reacts the unsupported catalyst presoma suspension B for obtaining green for 10 hours at 93 DEG C later.
It takes 60mL (butt is 4 grams) solution A in beaker, 165mL (butt is 9.3 grams) B is mixed with, is obtained later
Mixture C, mixture C are packed into crystallizing kettle after stirring 6 hours, take out within crystallization 12 hours for 160 DEG C under stirring, product exists
100 DEG C drying 12 hours, obtain modified non-loading type NiMo catalyst precursor powder.Precursor powder is using tabletting
Mode forms, and roasts 4 hours at 350 DEG C, obtains non-loading type NiMo catalyst, be designated as Cat-2.
Embodiment 3
45.76 grams of tetrapropylammonium hydroxide (TPAOH) are weighed in beaker, the rear aluminium isopropoxide for being added 0.42 gram, stirring
42.52 grams of tetraethyl orthosilicates (TEOS) and 97.70 grams of deionized waters are slowly added dropwise after clarification, continues to stir, makes mixture again
Secondary change clarification, obtains ZSM-5 molecular sieve presoma stoste, ZSM-5 molecular sieve presoma stoste 160 DEG C of crystallization 3 in crystallizing kettle
It is taken out after hour, obtains ZSM-5 molecular sieve nano-cluster solution A.
Weigh 43.62 grams of nickel nitrates and 17.66 grams of ammonium molybdates dissolve respectively after be added sequentially in three-necked flask, stirring is simultaneously
Heating makes mixture become clarification, and ammonium hydroxide is slowly added into when temperature reaches 93 DEG C, and solution becomes cloudy first, continues that ammonium hydroxide change is added dropwise
Stop being added dropwise when clarification, solution reacts the unsupported catalyst presoma suspension B for obtaining green for 10 hours at 93 DEG C later.
It takes 60mL (butt is 4 grams) solution A in beaker, 284mL (butt is 16.0 grams) B is mixed with, is obtained later
To mixture C, mixture C is packed into crystallizing kettle after stirring 6 hours, takes out within crystallization 12 hours for 160 DEG C under stirring, product exists
100 DEG C drying 12 hours, obtain modified non-loading type NiMo catalyst precursor powder.Precursor powder is using tabletting
Mode forms, and roasts 4 hours at 350 DEG C, obtains non-loading type NiMo catalyst, be designated as Cat-3.
Embodiment 4
This example demonstrates that catalyst activity evaluation method.
With 3wt%CS2/ petroleum ether solution is presulfurization reagent, liquid hourly space velocity (LHSV) 6h-1, hydrogen-oil ratio 300:1, pressure is
3Mpa, temperature are 330 DEG C and carry out presulfurization 8 hours to catalyst.The stage of reaction includes DBT hydrodesulfurization and naphthalene adds hydrogen, reaction
Condition are as follows: (1) using 1wt%DBT/ petroleum ether solution as raw material, liquid hourly space velocity (LHSV) 10h-1, hydrogen-oil ratio 300:1, pressure is
3Mpa, temperature are 280 DEG C, catalyst amount 5mL.(2) using 8wt% naphthalene/petroleum ether solution as raw material, liquid hourly space velocity (LHSV) 4h-1,
Hydrogen-oil ratio is 300:1, and pressure 4.0Mpa, temperature is 360 DEG C, catalyst amount 5mL.
The pyridine that Fig. 1 gives ZSM-5 molecular sieve base non-supported hydrogenation catalyst prepared by the present invention is infrared (Py-IR)
Spectrogram.It can therefrom be evident that the unsupported catalyst L acid prepared using the method for the present invention and B acid are remarkably reinforced.
Fig. 2 gives the NH of ZSM-5 molecular sieve base non-supported hydrogenation catalyst prepared by the present invention3- TPD figure.It therefrom can be very bright
Aobvious finds out that the total acid content of the unsupported catalyst prepared using the method for the present invention is remarkably reinforced.
Table 1 gives DBT and naphthalene hydrogenation reaction result in different catalysts.There it can be seen that unsupported catalyst
It is had increased slightly through the modified hydrogenation activity of type ZSM 5 molecular sieve nano-cluster, especially its cracking activity significantly improves.
DBT and naphthalene hydrogenation reaction result in 1 different catalysts of table
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (4)
1. a kind of method of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst, it is characterised in that described urges
Agent is formed as prepared by the method including including the following steps:
(1) presoma of ZSM-5 molecular sieve is synthesized first in alkali free metal ion system.Stoichiometry is taken by a certain percentage
Suitable aluminium isopropoxide is added later, is slowly added into positive silicic acid after stirring clarification in beaker for tetrapropylammonium hydroxide (TPAOH)
Tetra-ethyl ester (TEOS) and deionized water continue to stir certain time, so that mixture is become clarification again, before obtaining ZSM-5 molecular sieve
Body stoste is driven, presoma stoste obtains ZSM-5 molecular sieve nano-cluster solution A in suitable temperature crystallization certain time.
(2) a certain proportion of ammonium molybdate, nickel nitrate are added in the three-necked flask containing deionized water, stirring and heating makes to mix
It closes object and becomes clarification, when temperature reaches 90~100 DEG C, start that ammonium hydroxide is slowly added dropwise, continue dropwise addition ammonium hydroxide when precipitating to molten
Liquid stops being added dropwise when becoming clarification again, and solution is stirred to react 2~20 hours at 90~100 DEG C of constant temperature, obtains the suspension of green
B。
(3) it takes certain proportion A liquid to be added in B liquid, is stirred into slurries C.
(4) slurries C is packed into crystallizing kettle, is taken out within crystallization 10~24 hours for 90~180 DEG C under stirring, filters, wash, produce
Product are 10~24 hours dry at 60~100 DEG C, obtain catalyst precursor powder, precursor powder can using it is conventional at
Type method is formed, such as tabletting, extrusion etc., roasts 3~5 hours at 300~550 DEG C, it is non-negative to obtain ZSM-5 molecular sieve base
Load type NiMo catalyst.
2. ZSM-5 molecular sieve base non-supported hydrogenation catalyst according to claim 1, nickel molybdenum molar ratio is 1~2:
1, active metal NiMo content (based on oxide) are 50wt%~90wt%, and ZSM-5 molecular sieve content (based on butt) is
5wt%~50wt%.
3. method for preparing catalyst according to claim 1 synthesizes the molar ratio of material of A liquid are as follows: 1.0SiO2: 0.003~
0.005Al2O3: 0.45~0.5TPAOH:30~40H2O。
4. the ZSM-5 molecular sieve base non-supported hydrogenation catalyst prepared method according to claim 1, can be used for petroleum
The hydrofinishing of fraction, aromatic hydrocarbons etc. and aromatic hydrocarbons and cycloalkane plus hydrogen open loop, the reaction such as be hydrocracked.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301285A (en) * | 2021-05-08 | 2022-11-08 | 中国石油天然气股份有限公司 | Molecular sieve nanocluster modified non-supported Ni-Mo hydrogenation catalyst, and preparation method and application thereof |
| CN115845848A (en) * | 2022-12-08 | 2023-03-28 | 中国石油大学(华东) | Copper-based catalyst for preparing high-carbon alkane by grease hydrogenation and preparation method thereof |
| CN116060081A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Silicon capturing catalyst and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778872A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst containing molecular sieve |
| CN101088614A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aromatized eutectic superfine zeolite grain catalyst and its prepn process and application |
| CN101255356A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Unsupported catalyst and preparation method thereof |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101837299A (en) * | 2009-03-18 | 2010-09-22 | 中国石油天然气股份有限公司 | Catalyst for catalytic gasoline hydrogenation modification and preparation method thereof |
| US20110042267A1 (en) * | 2008-02-08 | 2011-02-24 | Jx Nippon Oil & Energy Corporation | Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oil |
| CN103122256A (en) * | 2013-01-29 | 2013-05-29 | 沈阳三聚凯特催化剂有限公司 | Application of W-Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| WO2014158843A1 (en) * | 2013-03-14 | 2014-10-02 | Exxonmobil Research And Engineering Company | Methods for producing basestocks from renewable sources using dewaxing catalyst |
| CN104941695A (en) * | 2015-06-08 | 2015-09-30 | 清华大学 | Nano ZSM-5 molecular sieve based catalyst and preparation and use methods |
| CN106215973A (en) * | 2016-08-12 | 2016-12-14 | 清华大学 | A kind of modified ZSM-5 5 molecular sieve catalyst method of preparation and use |
| CN106925338A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | Sulfur-carrying type hydrodesulfurization modification catalyst and preparation method thereof |
| CN108097294A (en) * | 2017-12-15 | 2018-06-01 | 广东工业大学 | A kind of stratiform ZSM-5 catalyst and preparation method thereof and application |
| CN108212204A (en) * | 2018-03-23 | 2018-06-29 | 安徽理工大学 | A kind of microwave radiation technology methane directly prepares the catalyst and Catalytic processes of higher olefins |
| CN108273514A (en) * | 2018-01-18 | 2018-07-13 | 中国石油大学(华东) | A kind of preparation method with acid non-supported hydrogenation catalyst |
| CN108786903A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of olefin disproportionation catalyst and preparation method thereof |
-
2019
- 2019-01-11 CN CN201910025113.XA patent/CN109847793B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1778872A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst containing molecular sieve |
| CN101088614A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aromatized eutectic superfine zeolite grain catalyst and its prepn process and application |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| US20110042267A1 (en) * | 2008-02-08 | 2011-02-24 | Jx Nippon Oil & Energy Corporation | Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oil |
| CN101255356A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Unsupported catalyst and preparation method thereof |
| CN101837299A (en) * | 2009-03-18 | 2010-09-22 | 中国石油天然气股份有限公司 | Catalyst for catalytic gasoline hydrogenation modification and preparation method thereof |
| CN103122256A (en) * | 2013-01-29 | 2013-05-29 | 沈阳三聚凯特催化剂有限公司 | Application of W-Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| WO2014158843A1 (en) * | 2013-03-14 | 2014-10-02 | Exxonmobil Research And Engineering Company | Methods for producing basestocks from renewable sources using dewaxing catalyst |
| CN104941695A (en) * | 2015-06-08 | 2015-09-30 | 清华大学 | Nano ZSM-5 molecular sieve based catalyst and preparation and use methods |
| CN106925338A (en) * | 2015-12-30 | 2017-07-07 | 中国石油天然气股份有限公司 | Sulfur-carrying type hydrodesulfurization modification catalyst and preparation method thereof |
| CN106215973A (en) * | 2016-08-12 | 2016-12-14 | 清华大学 | A kind of modified ZSM-5 5 molecular sieve catalyst method of preparation and use |
| CN108786903A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of olefin disproportionation catalyst and preparation method thereof |
| CN108097294A (en) * | 2017-12-15 | 2018-06-01 | 广东工业大学 | A kind of stratiform ZSM-5 catalyst and preparation method thereof and application |
| CN108273514A (en) * | 2018-01-18 | 2018-07-13 | 中国石油大学(华东) | A kind of preparation method with acid non-supported hydrogenation catalyst |
| CN108212204A (en) * | 2018-03-23 | 2018-06-29 | 安徽理工大学 | A kind of microwave radiation technology methane directly prepares the catalyst and Catalytic processes of higher olefins |
Non-Patent Citations (3)
| Title |
|---|
| ZHENG SONIA LIN ET AL.: "Tetraalkylammonium salt/alcohol mixtures as deep eutectic solvents", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 张胜: "非负载型Ni-Mo-W加氢催化剂制备工艺与性能评价", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 陈家镛: "《湿法冶金手册》", 30 September 2005, 冶金工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301285A (en) * | 2021-05-08 | 2022-11-08 | 中国石油天然气股份有限公司 | Molecular sieve nanocluster modified non-supported Ni-Mo hydrogenation catalyst, and preparation method and application thereof |
| CN116060081A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Silicon capturing catalyst and preparation method thereof |
| CN115845848A (en) * | 2022-12-08 | 2023-03-28 | 中国石油大学(华东) | Copper-based catalyst for preparing high-carbon alkane by grease hydrogenation and preparation method thereof |
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