CN101255356A - Unsupported catalyst and preparation method thereof - Google Patents
Unsupported catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101255356A CN101255356A CNA2008101043028A CN200810104302A CN101255356A CN 101255356 A CN101255356 A CN 101255356A CN A2008101043028 A CNA2008101043028 A CN A2008101043028A CN 200810104302 A CN200810104302 A CN 200810104302A CN 101255356 A CN101255356 A CN 101255356A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- metal
- catalyst
- preparation
- specific surface
- 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.)
- Granted
Links
Abstract
Disclosed are a unsupported catalyst for deeply hydrofinishing of intermediate distillate and method for making the same, particularly a catalyst particle with nanometer pore and relatively high specific surface area obtained by urea melt reaction. The most outstanding technical feature of the invention is that by adopting synthesis technique of urea melt reaction, metal is free of loss, prepared metal composite has nanometer pore and relatively high specific surface area, and could provide abundant catalytic hydrogenation activity bits, and the inventive catalyst has much higher catalytic hydrogenation activity comparing with conventional supported catalyst because of this. Meanwhile, the invention is simple in process, easy to operate, fast in reaction, suitable for industrial production.
Description
Technical field
The present invention relates to the unsupported catalyst and the preparation thereof of the super deep hydrofinishing of a kind of intermediate oil.It is the improvement that belongs to hydrogenization catalyst preparation method, specifically react by urea melting, obtain a kind of catalyst particles that self has nano pore and high specific surface area, extruded moulding obtains a kind of so-called unsupported catalyst that is different from the conventional negative supported catalyst then, compare with the conventional negative supported catalyst, unsupported catalyst has higher catalytic activity.
Background technology
In recent years, crude oil poor qualityization tendency is obvious day by day in the world wide, and sulphur, nitrogen and aromaticity content increase day by day in the petroleum products, and more and more stricter environmental requirement and the contradiction between this reality are more sharp-pointed.The China's oil product particularly diesel product to have more than 1/3rd be by catalytic cracking process production, widespread usage along with the heavy oil fluid catalytic cracking technology, catalytically cracked material becomes gradually heavily, becomes bad, the character that makes catalytic cracking diesel oil is variation day by day, sulphur, nitrogen and aromaticity content increase day by day in the diesel oil, and cetane value significantly reduces.At present, for slowing down topsoil, countries in the world have proposed more strict requirement to the quality index of vehicle fuel, and the sulphur in the derv fuel oil index, nitrogen and aromaticity content reduce greatly, and cetane value requires to significantly improve.At present, to the diesel oil standard sulphur content, the America and Europe is limited in 150～350ug/g, to be limited in 50ug/g to 2005, European Union, the U.S., Japan and other countries are advocated energetically recently and are carried out in the near future implementing ultralow diesel oil standard (ULSD), require the sulphur content in the derv fuel oil to be limited on 10～15ppm level exactly.
As everyone knows, hydrogenation technique is to improve oil quality one of the most effective process means, hydrogenation catalyst is a technology the most important and crucial in the hydrogenation technique, therefore, domestic and international many oil and petro-chemical corporation all are devoted to the improvement to existing hydrogenation catalyst at present, in the hope of continually developing out the better hydrotreating catalyst of performance.In conjunction with the state of the art both domestic and external, poor ignition quality fuel (for example: the Medium diesel oil of high-sulfur cycloalkyl straight-run diesel oil, coker gas oil, catalytic cracking diesel oil or above raw material) have only through could be as the blend component of derv fuel oil behind the deep hydrofinishing (desulfurization, denitrogenation, rare hydrocarbon, aromatic hydrocarbons are saturated), so the hydrotreating catalyst that is specially adapted to the super deep hydrofinishing of poor ignition quality fuel is one of catalizer variety of being badly in need of of present petroleum refining industry.
Traditional Hydrobon catalyst generally is made up of the metal with hydrogenating function or metal oxide and carrier, metal component commonly used is group vib and VIII metal, for example cobalt, molybdenum, nickel, tungsten etc., this class catalyzer generally is carried on the carrier metal active component by pickling process, because be subjected to metal load quantitative limitation (general active metal oxide charge capacity is less than 30%), its catalytic activity is comparatively gentle.Certainly the character by optimization of preparation and change carrier improves activity of such catalysts and selectivity, make it more appropriate to the deep hydrofinishing of poor-quality diesel-oil by cut fraction.This type of technology is such as US4,188, having introduced a kind of in 281 is active constituent with VIB, VIIB, VIII family metal, with faujusite (adding small amounts aluminium is caking agent) is the hydrotreating catalyst of carrier, this catalyzer can be used for mink cell focus hydrotreatment process, tail oil after the hydrotreatment is as the raw material of steam cracking production ethene, and ethylene yield has raising by a relatively large margin; US3, the dry and roasting with alumina sol makes the carrier that pore volume is 0.15～0.45ml/g in 779,903, floods nickel, tungsten and drying then, roasting makes the catalyzer that contains nickel oxide 10～18 heavy %, Tungsten oxide 99.999 25～40 heavy % and fluorine 1～9 heavy %; US4,330,395 to disclose a kind of be raw material with tungsten compound and aluminum compound, by evaporate to dryness, roasting, with the nickel compound dipping, vulcanizes and fluoridize with sulphur compound and fluorine cpd then, prepares a kind of middle runnings oil hydrogenating treatment catalyst; CN85,104, the high single diaspore of the method preparation of 438B employing aluminum alkoxide or alkyl aluminum hydrolysis is prepared a kind of hydrotreating catalyst that contains nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy % as the precursor of support of the catalyst; CN1,105,053 discloses a kind of catalyzer that is applicable to the heavy distillate hydrotreatment, this catalyzer consist of nickel oxide 1～5 heavy %, Tungsten oxide 99.999 15～38 heavy %, fluorine 1～9 heavy %, its carrier is a kind ofly at high temperature to handle the modified aluminas that obtains with air and water vapour; CN1,169,336A discloses the catalyzer that a kind of distillate hydrogenation is handled, the nickel oxide 1～5 that consists of of this catalyzer weighs %, Tungsten oxide 99.999 15～38 heavy %, fluorine 1～9 heavy %, all the other are aluminum oxide, this alumina supporter is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50, wherein aperture aluminum oxide micro-pore diameter accounts for the aluminum oxide of total pore volume more than 95% less than the pore volume in the hole of 8nm, and the pore volume in macroporous aluminium oxide micro-pore diameter 6～60nm hole accounts for the aluminum oxide of total pore volume more than 70%.
As can be seen, though above-mentioned catalyzer has carried out modification to carrier character, its hydrogenation activity still can not satisfy the requirement to the super deep hydrofinishing of the special poor ignition quality fuel of middle distillate.In order to improve activity of hydrocatalyst, some new catalyst technologies of preparing begin to be used for to produce in recent years, such as, US 6,652, and 738 and US 6,534,437 grades disclose a kind of preparation method of body catalyst, adopt hydro-thermal synthetic method, obtain a kind of mixed metal compositions, be used to prepare hydrogenation catalyst, US 4,596, and 785 disclose a kind of method of using the metallic sulfide coprecipitation method to prepare hydrogenation catalyst.Though the prepared catalyzer of these methods can improve hydrogenation activity, the shortcoming that these methods exist mainly is: (1) hydrothermal synthesis method or coprecipitation method can cause the part metals loss, and metal recovery rate is low; (2) resulting mixed metal compositions pore structure specific surface area is little, and the using rate of metal of catalyzer is not high, causes the catalyzer cost to increase.
Summary of the invention
The unsupported catalyst that purpose of the present invention proposes the super deep hydrofinishing of a kind of intermediate oil with regard to being to avoid the deficiencies in the prior art part, this method can overcome the shortcoming of hydro-thermal reaction and coprecipitation reaction method, improve metal recovery rate, increase the specific surface area of catalyzer, thereby can improve the hydrogenation activity of catalyzer greatly.This has the catalyzer of high hydrogenation activity, and its active constituent is made of one or both metal ingredients among one or both and Mo, the W that comprise among Co, the Ni, and its active metal oxide content is at 30～100wt%.The concrete preparation process of catalyzer of the present invention is as follows:
(1) metal component precursor
The catalyzer of high hydrogenation activity provided by the present invention, its VIII family metal is generally metals such as Fe, Co, Ni, be preferably Ni and Co, its metal oxide content is generally 10～90%, be preferably 20-80%, its group vib metal is generally metals such as Mo, W, Cr, is preferably Mo and W, its metal oxide content is generally 1～90%, is preferably 20-80%.Used metal precursor can be one or both of VIII family metal, adds one or both of group vib metal, such as Co-Mo, and Ni-Mo, Ni-W, Co-Ni-W, Ni-Mo-W, Co-Mo-W and Co-Mo-Ni-W etc.According to this Preparation of catalysts method provided by the invention, described reactive metal precursor is salt, oxide compound and the acids etc. that comprise reactive metal, metallic salt such as, the carbonate of Co, Mo, Ni, W, nitrate, phosphoric acid salt, Citrate trianion, tungstate, molybdate etc.
(2) urea melting reaction
The method for preparing catalyst of high hydrogenation activity provided by the present invention, be that the above metal component precursor and mixed being incorporated under the urea melting state of urea are reacted, remove unnecessary urea, obtain a kind of catalyst particles that self has nano pore and high specific surface area, the amount of its used urea and the mass ratio of metallics are 1～5/1, be preferably 2～3/1, its described hybrid reaction method, can be to grind, stir, common methods such as ultra-sonic dispersion, its described temperature of reaction is generally 100～200 ℃, is preferably 120～150 ℃, reaction times is 2～10 hours, is preferably 4～6 hours.Its described a kind of catalyst particles that self has nano pore and high specific surface area, its channel diameter is 3～10nm, its BET method specific surface area is 100～450m
2/ g is generally 150～350m
2/ g.
The most outstanding technical characterictic of the present invention is owing to adopted the urea melting reactive synthesis technique, speed of response is fast, make prepared metal compound particles self have flourishing duct and bigger specific surface area, himself just can provide abundant catalytic hydrogenation activity position.Just for this reason, make catalyzer of the present invention have the catalytic hydrogenation activity more much higher than conventional negative supported catalyst.
(3) shaping of catalyst
According to this Preparation of catalysts method provided by the invention, catalyzer can be a powder type, also can carry out moulding, its moulding process can add certain binding agent, its add-on is 0～50%, be preferably 10～30%, binding agent can be selected industrial kind commonly used for use, such as silicon sol, aluminium colloidal sol etc.Wherein said forming method comprises methods such as compressing tablet, balling-up or extrusion, preferably adopts the method for extruded moulding.
(4) activation of catalyzer
According to this Preparation of catalysts method provided by the invention, its said catalyzer can be through calcination process, and maturing temperature is that 200～500 ℃, time are 2～8 hours; Preferably maturing temperature is that 250-400 ℃, time are 4～6 hours.
According to this Preparation of catalysts method provided by the invention, its described catalyzer must be handled through prevulcanized, and curing temperature is 200～450 ℃, be preferably 300～400 ℃, curing time is 8～48 hours, is preferably 10～25 hours, hydrogen to oil volume ratio is 100-800, is preferably 300～500.
That catalyzer provided by the invention can be used for comprising is light,, the oil product of last running wet goods surpasses Deep Hydrotreating, and other suitable hydrotreatment occasions, such as: the hydrogenation of hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), alkene and aromatic hydrocarbons is saturated etc., and the processing condition that are suitable for are conventional hydrogenation technique condition.This catalyzer can be regulated as required and make dissimilar solid particulate matters, such as being used for fixing hydrogenation technique processes such as bed, fluidized-bed and suspension bed.
Embodiment
Come enumeration technical characterstic of the present invention below in conjunction with embodiment.
Embodiment 1
Present embodiment illustrates Preparation of catalysts method of the present invention.
Take by weighing the molybdic oxide (0.1 mole of Mo) of 14.2 grams, the wolframic acid (0.1 mole of W) of 25.0 grams, the basic nickel carbonate (0.3 mole of Ni) of 41.5 grams, 161.4 gram urea joins in the there-necked flask, and the adding less water is uniformly dispersed it, place oil bath in 130 ℃ of stirring reactions 4 hours, while hot reactant is poured in the pallet and cooled off, with pulverizer cooled product is pulverized, placed 150 degree baking ovens to dry, make unnecessary urea decomposition.Taking by weighing pressed powder 30% heavy pseudo-boehmite adds 10% dilute nitric acid solution and makes aluminium colloidal sol, pressed powder is joined in the aluminium colloidal sol, with become pasty state, warp mixes and pinches, extrusion, make the bar of diameter 1.6mm, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃ under infrared lamp, 400 ℃ of roasting 5h make unsupported catalyst F1 in muffle furnace.The BET surface-area of this catalyzer is 232.0m
2/ g, pore volume 0.35cm
3/ g, mean pore size 5.8nm.
Embodiment 2
Present embodiment illustrates Preparation of catalysts method of the present invention.
Get the ammonium molybdate (0.1 mole of Mo) of 17.6 grams, the ammonium metawolframate (0.1 mole of W) of 26.4 grams, the basic nickel carbonate (0.3 mole of Ni) of 41.5 grams, 171.0 gram urea joins in the there-necked flask, and the adding less water is uniformly dispersed it, place oil bath in 130 ℃ of stirring reactions 4 hours, while hot reactant is poured in the pallet and cooled off, with pulverizer cooled product is pulverized, placed 150 degree baking ovens to dry, make unnecessary urea decomposition.Taking by weighing the heavy pseudo-boehmite of pressed powder 30%, to add concentration be that the dilute nitric acid solution of 10wt% is made aluminium colloidal sol, pressed powder is joined in the aluminium colloidal sol, with become pasty state, warp mixes and pinches, extrusion, make the bar of diameter 1.6mm, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃ under infrared lamp, 400 ℃ of roasting 5h make catalyzer F2 in muffle furnace.The BET surface-area of this catalyzer is 240.6m
2/ g, pore volume 0.31cm
3/ g, mean pore size 5.5nm.
Embodiment 3
Present embodiment illustrates Preparation of catalysts method of the present invention.
Take by weighing the molybdic oxide (0.1 mole of Mo) of 14.2 grams, the wolframic acid (0.1 mole of W) of 25.0 grams, the basic nickel carbonate (0.2 mole of Ni) of 27.6 grams, 133.6 gram urea joins in the there-necked flask, and the adding less water is uniformly dispersed it, place oil bath in 130 ℃ of stirring reactions 4 hours, while hot reactant is poured in the pallet and cooled off, with pulverizer cooled product is pulverized, placed 150 degree baking ovens to dry, make unnecessary urea decomposition.Taking by weighing the heavy pseudo-boehmite of pressed powder 30%, to add concentration be that the dilute nitric acid solution of 10wt% is made aluminium colloidal sol, pressed powder is joined in the aluminium colloidal sol, with become pasty state, warp mixes and pinches, extrusion, make the bar of diameter 1.6mm, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃ under infrared lamp, 400 ℃ of roasting 5h make catalyzer F3 in muffle furnace.The BET surface-area of catalyzer is 200.5m
2/ g, pore volume 0.30cm
3/ g, mean pore size 6.8nm.
Embodiment 4
Present embodiment explanation comparative catalyst's preparation method.
Take by weighing the molybdic oxide (0.1 mole of Mo) of 14.2 grams, the wolframic acid (0.1 mole of W) of 25.0 grams, the basic carbonate nickel by powder (0.2 mole of Ni) of 27.6 grams, adding 20 gram pseudo-boehmites mixes, the dilute nitric acid solution that adds concentration then and be 10wt% with become pasty state, warp mixes and pinches, extrusion, make the bar of diameter 1.6mm, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃ under infrared lamp, 400 ℃ of roasting 5h make the comparative catalyst in muffle furnace.
Embodiment 5
Present embodiment illustrates the evaluation method of catalyzer of the present invention
The catalyst activity evaluation is to carry out in anti-in that the 10mL high pressure is little.The model compound raw material consists of: 10% naphthalene, 2% dibenzothiophene (DBT) (about 3630ppm sulphur), 2% quinoline (about 2170ppm nitrogen), 86% toluene.Raw material adopts ram pump to pump into, and hydrogenation products is after high-pressure separator (cold high score) and light pressure separator are isolated liquids and gases, and the product liquid inflow connects the sample jar.In the time of 120 ℃, begin to pump into and contain CS
2Hexanaphthene (3wt%) carries out prevulcanized, is warmed up to 360 ℃, vulcanizes 10 hours, and liquid hourly space velocity is 2.0h
-1Be cooled to temperature of reaction then, begin into raw material (model compound), stable reaction was taken a sample after 5 hours, analyzed with gas chromatograph (Varian3800 capillary chromatograph, fid detector).Reaction conditions: 340 ℃, liquid hourly space velocity is 2.0h
-1, hydrogen-oil ratio: 300/1, reaction pressure: 2.0MPa.The reaction evaluating of several catalyzer is as a result shown in the table 1.
Hydrogenating desulfurization, hydrodenitrification and the aromatic hydrogenation activity of the hydrogenation catalyst that presentation of results the present invention of table 1 is prepared is significantly higher than the comparative catalyst of traditional kneading method preparation.
Table 1 catalyst activity evaluation result of the present invention
| Catalyzer | HDS，％ | HDN，％ | HDAr，％ |
| F1 | 99.0 | 87.9 | 55.9 |
| F2 | 100.0 | 86.0 | 52.1 |
| F3 | 99.6 | 88.2 | 54.1 |
| The comparative catalyst | 95.8 | 63.5 | 39.1 |
The invention effect
Compared with prior art, the most outstanding technical characterictic of the present invention is to have adopted the urea melting reactive synthesis technique, the metal free of losses, prepared metallic combination composition granule self has flourishing duct and larger specific area, himself just can provide abundant catalytic hydrogenation activity position, namely for this reason, so that catalyst of the present invention has the catalytic hydrogenation activity more much higher than conventional negative supported catalyst. Simultaneously, the inventive method is simple, easily operation, and reaction speed is fast, is fit to industrialized mass production. That catalyst provided by the invention can be used for comprising is light,, the oil product of heavy distillat wet goods surpasses Deep Hydrotreating, and other suitable hydrotreatment occasions, such as: the hydrogenation of hydrodesulfurization, hydrodenitrogeneration, HDM, alkene and aromatic hydrocarbons is saturated etc., and the process conditions that are suitable for are conventional hydrogenation technique condition. This catalyst can be regulated as required and make dissimilar solid particulate matters, such as being used for the hydrogenation process such as fixed bed, fluid bed and suspension bed.
Claims (3)
1. the preparation method of a unsupported catalyst, this catalyzer is several metal component precursor and urea to be mixed to be incorporated in react resultant a kind of catalyst particles that self has nano pore and high specific surface area under the molten state.It is characterized in that its metal component can be that one or both metal ingredients among one or both and Mo, the W among Co, the Ni constitute, these metal components can use its metal oxide, salt, metal precursor such as acid; It reacts under molten state, is meant that in temperature of reaction be 100～200 ℃, and the reaction times is to react in 2～10 hours, and its reactant is dispersed in molten state urea the inside; With the metal oxide timing, the mass ratio of the amount of its urea and the total material of metal is 1～5/1; Resulting catalyzer is measured through the BET method, himself has the catalyst particles of nano pore and high specific surface area, and its channel diameter is 3～10nm, and specific surface area is 100～450m
2/ g,
2. the preparation method of a kind of unsupported catalyst according to claim 1 is characterized in that described catalyzer can be a powder type, also can carry out forming processes; Its moulding process is the binding agent of adding 10～30%, and binding agent can be silicon sol, aluminium colloidal sol etc., and its forming method comprises methods such as compressing tablet, balling-up or extrusion.
3. the preparation method of a kind of unsupported catalyst according to claim 1 is characterized in that catalyzer can carry out calcination process, and its maturing temperature is that 200～500 ℃, time are 2～8 hours; When catalyzer is used for hydrogenation, can also carry out prevulcanized and handle, its curing temperature is 200～450 ℃, and curing time is 8～48 hours, and hydrogen to oil volume ratio is 100～500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101043028A CN101255356B (en) | 2008-04-17 | 2008-04-17 | Unsupported catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101043028A CN101255356B (en) | 2008-04-17 | 2008-04-17 | Unsupported catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101255356A true CN101255356A (en) | 2008-09-03 |
| CN101255356B CN101255356B (en) | 2012-07-18 |
Family
ID=39890474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101043028A Active CN101255356B (en) | 2008-04-17 | 2008-04-17 | Unsupported catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101255356B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989526A (en) * | 2012-12-25 | 2013-03-27 | 东北石油大学 | Method of preparing body catalyst for distillate oil depth hydrofining by utilizing microwave method |
| CN103285886A (en) * | 2013-03-07 | 2013-09-11 | 中国石油大学(华东) | Catalyst for synthesis of decalin by one-step hydrogenation of naphthalene and method thereof |
| WO2015007230A1 (en) | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | Iron-based hydrogenation catalyst and applications thereof |
| CN109847793A (en) * | 2019-01-11 | 2019-06-07 | 中国石油大学(华东) | A kind of method of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019019B (en) * | 1985-12-05 | 1992-11-11 | 东北师范大学 | Process for synthesizing cobalt phthalocyanine desulfating catalyst |
| US6534437B2 (en) * | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| CN1251797C (en) * | 2003-10-24 | 2006-04-19 | 中国石油化工股份有限公司 | Prepn process of hydroprocessing catalyst |
-
2008
- 2008-04-17 CN CN2008101043028A patent/CN101255356B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989526A (en) * | 2012-12-25 | 2013-03-27 | 东北石油大学 | Method of preparing body catalyst for distillate oil depth hydrofining by utilizing microwave method |
| CN103285886A (en) * | 2013-03-07 | 2013-09-11 | 中国石油大学(华东) | Catalyst for synthesis of decalin by one-step hydrogenation of naphthalene and method thereof |
| WO2015007230A1 (en) | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | Iron-based hydrogenation catalyst and applications thereof |
| US10335773B2 (en) | 2013-07-18 | 2019-07-02 | China University of Petroleum—Beijing | Fe-based hydrogenation catalyst and use thereof |
| CN109847793A (en) * | 2019-01-11 | 2019-06-07 | 中国石油大学(华东) | A kind of method of eutectic method synthesis ZSM-5 molecular sieve base non-supported hydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101255356B (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104383923B (en) | A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof | |
| CN104918698B (en) | A kind of iron-based hydrogenation catalyst and application thereof | |
| CN104437518B (en) | A kind of catalyst for selectively hydrodesulfurizing and its preparation and application | |
| US20110124497A1 (en) | Catalyst and process for the manufacture of ultra-low sulfur distillate product | |
| CN103184069B (en) | Inferior coker gas oil hydrotreatment method | |
| CN102580758B (en) | NiO-MoO3/ TiO2 catalyst and preparation method thereof | |
| CN102909027A (en) | Preparation method of catalyst by ultralow-sulfur hydrofining | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN100515565C (en) | Preparation for high dispersing, amorphous, high efficient novel desulfate catalyst | |
| CN103769179A (en) | Preparation method of residual oil hydro-treatment catalyst | |
| CN101255356B (en) | Unsupported catalyst and preparation method thereof | |
| CN101280216B (en) | Method for producing ultra-low sulfur diesel | |
| CN103059934B (en) | A kind of hydro-upgrading pour-point depressing method taking into account diesel product quality | |
| CN103055952B (en) | Residual oil hydrotreating catalyst supporter and preparation method thereof | |
| CN102039140A (en) | Heavy oil hydrotreating catalyst as well as preparation method and application thereof | |
| KR20140079304A (en) | Residue hydrotreatment catalyst comprising vanadium, and its use in a residue hydroconversion process | |
| CN102423712B (en) | Preparation method of high-activity inferior diesel oil hydrorefining catalyst | |
| CN101816939A (en) | Catalyst for selective hydrodesulfurization and preparation method thereof | |
| CN101724442B (en) | Method for reducing octane number loss of gasoline deep hydrodesulphurization | |
| CN101306371B (en) | Selective hydrodesulfurization catalyst and its preparation method | |
| CN101280220B (en) | Method for producing good quality ethylene material by hydrogenation and dearomatization of benzin naphtha | |
| CN113680347A (en) | Hydrofining catalyst, preparation method thereof and application thereof in oil refining and aromatic ring saturation regulation | |
| CN101255357B (en) | Catalyst used for distillate oil deep hydrofinishing and preparation method thereof | |
| CN104096584B (en) | A kind of residual oil hydrocatalyst and preparation method thereof | |
| CN112742404A (en) | Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |